FULL PAPER

The Scope of Catalytic Asymmetric Hydroboration/Oxidation with Rhodium

Complexes of 1,1'-(2-Diarylphosphino-1-naphthyl)isoquinolines
Henri Doucet, Elena Fernandez, Timothy P. Layzell, and John M. Brown*[a]

Abstract: Preformed cationic Rh complexes of the title ligands are effective for the
asymmetric hydroboration/oxidation of vinylarenes at ambient temperature. These
vinylarenes may carry E- or Z-b substituents but not a substituents. Enantiomer
Keywords: asymmetric synthesis
excesses of up to 97 % can be obtained in the most favourable cases. The
catalysts hydroborations ligand
enantioselectivity is moderately sensitive to the structure of the ligand: the
effects rhodium
difurylphosphino ligand gave superior results for electron-poor styrenes and the
diphenylphosphino ligand the best results for electron-rich reactants. Mechanistic
aspects are discussed.

Introduction Results and Discussion

An early key experiment led to the eventual development of
rhodium-complex-catalysed hydroboration of alkenes.[1] This
work clearly demonstrated that Wilkinsons catalyst,
[ClRh(PPh3)3], reacts with a cyclic secondary boronate ester
by BH activation and that the h1-borylrhodium hydride
releases the reactant on further treatment with Et3SiH. The
first examples of this type of catalysis demonstrated the
potential power of the original experiment, and in particular
the use of catecholborane by Mannig and Nth has been the
model on which most further experimentation has been
based.[2, 3] Burgess and Ohlmeyer were the first to demon-
strate catalytic asymmetric hydroboration[4] and examples
permitting high enantiomer excess (ee > 90 %) were devel-
oped by Hayashis group, which employed rhenium BINAP
complexes for the asymmetric hydroboration of simple
styrenes.[5] Subsequently, other catalysts for asymmetric
hydroboration have been developed; both Togni[6] and
Brown[7] employed Rh complexes of heterotopic PN ligands
to give high enantiomer excesses in the hydroboration of
vinylarenes. This field has been reviewed recently.[8]
The present paper is concerned with comparisons between
ligands of the type 1,1'-(2-diarylphosphino-1-naphthyl)iso-
quinoline ligands[9] involved in Rh-complex-catalysed asym-
metric hydroboration, and in the effects of the aryl substitu-
ents on the efficiency and enantiomer excess observed.
[a] Dr. J. M. Brown, Dr. H. Doucet, Dr. E. Fernandez, Dr. T. P. Layzell
The Dyson Perrins Laboratory
South Parks Rd., Oxford OX1 3QY (England)
Fax: ( 44) 1865-275674
E-mail: bjm@ermine.ox.ac.uk
Our preliminary experiments[7] indicated that the parent
ligand 1 was a precursor to Rh complexes for the successful
catalytic hydroboration of simple vinylarenes. For the sim-
plest cases, the reaction proceeded with up to 94 % enantio-
selectivity and 99 % regioselectivity in toluene or THF at
ambient temperature. A preformed cationic rhodium complex
of structure 2 was required; the ligand also forms an air-
sensitive, homoleptic 2:1 complex that gives poor enantiose-
lectivity under the same conditions. Only vinylarenes give
interesting results (in terms of stereoselectivity) and the
detailed study reported here bears that constraint. Several
accessible structural variants of the parent ligand 1
(Scheme 1), were used in the investigations. The structures
of the ligand and the reactant were both changed in order to
probe for the relative importance of electronic and steric
effects. Although ligands 3, 5, 7 and 9 and their respective
rhodium complexes 4, 6, 8 and 10 (as CF3SO 3 or BF 4
complexes) are all available[10] and a full range of experiments
is reported; the subsequent discussion will emphasise the
results obtained with the difuranylphosphine complex 8 in
comparison with the parent complex 2, as this gave the most
interesting results. All the catalytic chemistry described here
involves hydroboration followed by peroxide oxidation to
give the corresponding secondary alcohol. Procedures have
been published recently for the conversion of the catechol-
boronate ester into a primary amine, whereby the ee is closely
comparable with that obtained in the H2O2 oxidation.[11]
Hydroboration of vinylarenes: The initial catalytic experi-
ments were carried out with freshly distilled catecholborane
in THF, although it was later found that comparable results

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Scheme 1. Ligands and Rh complexes used in the asymmetric hydro-
boration/oxidation reactions.
could be obtained in toluene solution. For the most part, the
reactions reported here were carried out on a 0.4 millimolar
scale with 1 mol % of catalyst; however, a hydroboration/
oxidation of styrene on a preparative scale, which employed
0.2 mol % catalyst 2 (as the S enantiomer), gave a marginally
higher ee. Thus, (S)-1-phenylethanol was produced in 75 %
isolated yield and 91.5 % ee after the standard oxidative work-
up (Scheme 2). In the experiments described here, the borane
was oxidised directly with alkaline H2O2 ; however, it has been
demonstrated that the borane may be distilled in vacuo with
Scheme 2. Protocol for the asymmetric hydroboration of styrene with
[((S)-QUINAP)Rh] (1 g scale). Reaction conditions: i) [LRh(C8H12)OTF]
(0.2 mol %; L (S)-1) in situ, THF, 20 8c; ii) H2O2 , OH.
minimal loss of enantiomeric purity.[12] For these simple
styrenes the regioisomeric purity of the crude reaction
product, assayed by chiral GC, is generally high; in those
cases in which these catalysts afforded a yield of the primary
alcohol of  5 % it could be attributed to impurities in the
alkene or deterioration of the catalyst.[13] As a general rule we
have found that impurities (peroxy-compounds?) in the
alkene can have a deleterious effect on the regioselectivity
and the enantioselectivity of the hydroboration reaction.
Hence distillation is recommended immediately before the
reaction. The results are grouped into those obtained with
electron-releasing aryl substituents (Table 1) and those ob-
Chem. Eur. J. 1999, 5, No. 4  WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999
1320 1330
Table 1. Hydroboration of electron-rich styrenes. Reaction conditions: tol-
uene, 2 h, ambient temperature, 1 mol % catalyst.
Alkene Catalyst sec-Al- ee[b] Con- Yield
cohol[a] figu-
ration
[a] The remainder is primary alcohol. [b] GC or NMR determination, see
Experimental Section. [c] First result: equimolar Rh/ligand (100 % reaction);
second result: 5 % excess ligand. [d] Catalyst as the triflate.
tained with electron-withdrawing substituents in the styrene
reactant (Table 2).
We will discuss the results of the hydroboration of electron-
rich styrenes first (Table 1). The regioselectivity of hydro-
boration/oxidation averages 96 % for seven reactants with
catalyst 2, and 94 % for six reactants with catalyst 8; the other
catalysts (4, 6 and 10) behaved similarly. In almost all cases the
best ee was obtained with catalyst 2, which is derived from the
parent ligand ArPPh2 . A single o-Me group is readily
accommodated without significant detriment in the yield or
the enantioselectivity. Incorporation of a second o-Me
(entry 1E) has a profound effect; perhaps this is because it
is no longer possible to achieve coplanarity of the arene and
alkene, which would inhibit the stabilisation of any h2-alkene
or h3-benzylrhodium intermediates. With this exception, the
results for alkylstyrenes are comparable to those obtained for
the parent. For the two alkoxystyrenes (entries 1G and 1H),
superior results to the parent are obtained with catalyst 2,
which indicates that there is some favouring of an electron-
rich alkene for maximum stereoselectivity. This is not
supported by the results in entry 1F, but it is possible that
the coordinating ability of the NMe2 group may affect the
outcome of the reaction.
Much clearer trends are observed in the hydroboration of
electron-deficient vinylarenes (Table 2), although the ees
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 FULL PAPER
Table 2. Hydroboration of electron-poor styrenes. Reaction conditions: tol-
uene, 2 h, ambient temperature, 1 mol % catalyst.
Alkene Catalyst sec-Al- ee[b] Con- Yield
cohol[a] figu-
ration
[a] The remainder is primary alcohol. [b] GC determination, see Experimental
section. [c] Catalyst as the triflate, THF.
observed were generally lower than those obtained with
electron-rich alkenes. In addition to the results reported in
Table 2, it was found that hydroboration of 3,5-bis-trifluor-
omethylstyrene was effected in low enantiomer excess (ee
5 % with catalyst 2 and 40 % with catalyst 8); the config-
uration of the product is inferred to be S for the latter case
simply by analogy. Although the ee obtained in the alcohol
produced by hydroboration/oxidation of 2,6-difluorostyrene
is low (< 15 %), it is much higher for the product from the
related 2,6-dichlorostyrene, which was, at best, 72 % (S) with
catalyst 8. With the exception of p-fluorostyrene (entry 2A),
catalyst 8 (derived from furylphosphine) gave higher enan-
tioselectivities than the parent catalyst 2 (derived from PPh2)
or any of the other catalysts employed. This superiority is very
clearly seen in meta- and ortho-substituted cases, for example,
the unsatisfactory ee of 63 % (entry 2E) with catalyst 2 which
compares with an ee of 89 % with catalyst 8; the difference for
the m-CF3 derivative (entry 2H) is equally striking. A detailed
discussion of this observation is given below.
Results obtained with other vinylarenes are presented in
Table 3. In general, the increase in steric demand around the
reaction site leads to lower regioselectivity. The example of
entry 3C possibly represents the limit of this methodology
with existing ligands; although the ee is reasonable with
catalyst 8, only 61 % of the secondary alcohol was obtained.
The result with vinylfuran (entry 3E) is surprisingly poor
1322  WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999
J. M. Brown et al.
Table 3. Hydroboration of vinylarenes. Reaction conditions: toluene, 2 h,
ambient temperature, 1 mol % catalyst.
Alkene Catalyst sec-Al- ee[b] Con- Yield
cohol[a] figu-
ration
[a] The remainder is primary alcohol. [b] GC or NMR determination, see
Experimental section. [c] Catalyst as the triflate, THF. [d] Similar results were
obtained with 2-vinyl-5-methylfuran. [e] Significant amounts of both primary
alcohol and ethylferrocene were obtained.
given the favourable cases of the electron-rich vinylarenes
discussed above, and may indicate a subtle interplay between
steric and electronic effects with the smaller 2-furyl residue
exerting a lower steric influence than that of phenyl or p-
methoxyphenyl.
The results obtained with b-substituted vinylarenes are
presented in Table 4. The hydroboration of both (Z)- and (E)-
propenylbenzene (entries 4A and 4B) gave high ees, which is
in contrast to the results obtained with the same reactants and
BINAP-Rh as the catalyst.[6] The likelihood of a rhodium-
hydride-driven cis trans isomerisation, observed in other
reactions of vinylarenes with secondary boranes,[14] is high and
certainly the reaction with trans-stilbene is much slower than
that of the cis-isomer (entries 4D and 4E). The combination of
an electron-rich arene and a beta-substituted alkene (en-
try 4F) gave the highest ee observed in the experiments: 97 %.
The reaction of indene deserves further comment, since we
had originally claimed an ee of 91 % and have been unable to
repeat that result, despite intensive effort. In addition, the
original ee determination was soundly based. A likely
explanation is that racemic indanol crystallises as a con-
glomerate[15] and the ee of a scalemic sample will be
influenced by sublimation, since the vapour will be racemic.[16]
Indeed, we have been able to raise the value of our original ee
of 76 % to 86 % simply by partial sublimation of the volatile
secondary alcohol during the removal of the solvent in a
rotary evaporator, which is in accord with several scattered
precedents in the literature.[17] The symmetrical alkene
acenaphthene (entry 4H) gave rise to the corresponding
secondary alcohol[18] with 86 % ee. Consistently good results
were obtained with 1,2-dihydronaphthalene (entry 4I), and
the ee of 96 % was reproduced on a gram scale with 0.2 %
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 Asymmetric Catalysis
Table 4. Hydroboration of b-substituted vinylarenes. Reaction conditions:
toluene, 2 h, ambient temperature, 1 mol % catalyst.
Alkene Catalyst sec-Alco- ee[b]
hol[a]
[a] The remainder is regioisomeric alcohol or hydrocarbon. [b] GC or NMR
determination, see Experimental section. [c] Catalyst as triflate, THF. [d] De-
termination of ee by proton NMR with [Eu(hfc)3].
catalyst. In this case the ultimate result is much superior to the
one reported previously;[7] consistent results were obtained
with the alkene purified immediately before reaction. In both
this and the case of 4-chromene (entry 4J) the parent catalyst
2 is superior to the furylphosphine analogue 8.
Mechanism and selectivity: There have been only a few direct
mechanistic studies of the hydroboration reaction catalysed
by rhodium complexes that have revealed details of the
catalytic cycle.[19] For vinylarenes, the weight of evidence
suggests that the cycle follows the pathway outlined in
Scheme 3, in which the hydride transfers regiospecifically to
give a benzylic borane, possibly h3, which in turn undergoes
reductive elimination with the formation of the hydroboration
product.[20] This representation is in agreement with a DFT
theoretical treatment.[21] Any attempt to rationalise the
enantioselectivity further must consider the hydride transfer
step in more depth, since the configuration of the new
stereogenic centre is set at that stage. Naturally, discussion
must be speculative, in the absence of structural information
on the key intermediates in this part of the catalytic cycle.
Whether there is any possibility of reversibility remains an
open question, since there are cases in which the configuration
of the alkene changes during catalytic turnover, implying that
hydride addition is reversible.[14] Whether this is due to the
true hydroboration catalyst or to a stray rhodium hydride
remains a matter for conjecture. Thus, in order to explain the
Chem. Eur. J. 1999, 5, No. 4  WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999
1320 1330
Con- Yield
figu-
ration
Scheme 3. The probable sequence of steps in the catalytic hydroboration
of a vinylarene to give the benzylic borane.
observed results, the following factors need to be taken into
consideration:
a) The stereochemical sense of hydroboration is quite general
and predictable for a range of vinylarenes.
b) Enantioselectivity seems to be unaffected by symmetry in
the alkene, since it is not important whether this is
prochiral or not.
c) Ligands in the QUINAP series have a significantly broader
profile of alkene reactants for which catalytic hydrobora-
tion is successful.
d) There are significant electronic effects on the enantiose-
lectivity of hydroboration such that electron-rich styrenes
are generally reduced with greater specificity than elec-
tron-poor styrenes.
e) These electronic effects can be augmented by ligand
substrate matching; the precise mechanism of this requires
explanation.
Before we address the results described here, two points are
worth raising. Firstly, the conventional catalyst precursor is a
rhodium cation or a rhodium halide. Catecholborane is a
reducing agent and will create a hydridorhodium species in
competition with hydroboration. The resting state of the
catalyst is difficult to determine because it is unstable in the
absence of excess alkene and it decomposes when the
turnover is complete. Since prior to bond formation, the
coordination sphere contains (in this case) a chelating ligand,
an alkene, a boryl and a hydride, there are several possibilities.
Secondly, the special role of catecholborane is relevant to the
discussion. It is far superior to other boranes in catalytic
hydroboration and it is likely that a combination of the
enhanced ease of BH addition and the favourable steric
profile of B-coordinated catecholborane both contribute to its
greater effectiveness; the latter, in particular, must be taken
into account in the design of models.
The fact that symmetrical alkenes (e.g., acenaphthene)
gave enantioselectivities comparable with prochiral alkenes
indicates that the alkene binding step does not define the
stereochemical outcome of catalysis, as would be expected if
that step was a reversible pre-equilibrium. It implies (c.f.
Scheme 4) a fixed spatial relationship between the RhH
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FULL PAPER J. M. Brown et al.

Table 4. For the corresponding

b-branched cases, ees of be-
tween 13 % and 42 % were
obtained with BINAP-Rh, in
reactions run at ambient tem-
perature. This indicates a great-
er tolerance of steric bulk by
the PN ligand, especially to-
wards the alkene b-position. It
can be rationalised in a broad
sense by the comparison of the
X-ray crystal structures of the
two ligands in metal-complexed
environments (Figure 1; the di-
Scheme 4. Comparisons of the stereochemical course of the addition of HX to alkenes: a) the asymmetric
phosphine, and particularly its
hydrogenation of dehydroamino acids with [(S)-BINAP]Rh; b) the asymmetric hydroboration of styrene with
[(S)-BINAP]Rh and c) the asymmetric hydroboration of styrene with [(S)-QUINAP]Rh. y-equatorial PPh groups, ex-
ert a much more pronounced
involved in transfer and the coordinated alkene; for a steric pressure on coordinated reactants. Since the cycle in
prochiral alkene, only one of the two coordinated diaster- catalytic hydroboration needs to accommodate both cate-
eomers contributes significantly to the catalytic turnover. cholborane and the alkene (potentially a much more crowded
environment than that in catalytic hydrogenation) the com-
QUINAP versus BINAP: In comparing these hydroboration parative void offered by the isoquinoline region of QUINAP
results with the earlier work of Hayashi, two points are permits greater tolerance towards reactant bulk. This cannot
apparent. Firstly, the product configuration is the same in both be the only factor, since the superficially similar phosphino-
cases, the R ligand gives rise to the R alcohol. Secondly, aryloxazoline Rh complexes[22] give comparatively poor results
reactions with BINAP require low temperatures for a in catalytic asymmetric hydroboration. In another series of
satisfactory ee; the best results were obtained in DME at ferrocene-based PN ligands, excellent enantioselectivity was
78 8C. At higher temperatures, the enantioselectivity is observed for styrene hydroboration when the pyrazole frag-
attenuated; styrene gave 1-phenylethanol with 57 % ee in ment was electron-rich, with a pronounced electronic effect.[6]
THF at 25 8C. The only other substrates for which an ee of
> 90 % has been demonstrated are 4-methylstyrene (94 %) Substituent effects: The enantioselectivity observed in the
and 4-chlorostyrene (91 %), which were obtained at 78 8C. hydroboration of substituted styrenes depends on the ring
Higher temperatures were required for the hydroboration of substituent. For catalyst 2, and omitting the result with p-
2-methoxy- and 2-chlorostyrene where the ee of the secondary NMe2 , the results range from 94 % ee for p-OMe to 37 % for
alcohol was 82 % and 72 %,
respectively. In contrast, the
QUINAP-based results were
obtained at room temperature
and the effect of cooling was
found to be deleterious. An
interesting facet is the sensitiv-
ity to the rhodium:ligand ratio;
it is particularly apparent in
those cases in which the alkene
reactivity is low. We have veri-
fied that a 2:1 ligand:Rh com-
plex can be formed, and that
hydroboration of styrene in its
presence occurs with low enan-
tioselectivity. An example from
the present set of results is
given by entry 1E in Table 1.
It is evident that the range of
alkenes for which we have
demonstrated an effective
asymmetric hydroboration is
much wider for QUINAP than
Figure 1. Comparison of the steric profiles of PP and PN ligands in molecular fragments taken from X-ray
for BINAP; specific examples structural data: a) plan view of (BINAP)M, b) elevation view of (BINAP)M, c) plan view of (QUINAP)M,
are entries 4A, 4B, 4G and 4I in d) elevation view of (QUINAP)M.

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Asymmetric Catalysis
m-CF3 . A plot of log10 (R/S) versus Hammett s gives a
modestly reasonable straight line for eleven determinations
(Figure 2), which suggests a simple trend related to the
Figure 2. Linear free-energy plot relating the enantioselectivity of hydro-
boration in monosubstituted styrenes with the parent QUINAP complex 2
to the Hammett s values for the m or p substituents.
inductive effect of the substituent. A much narrower range of
results is obtained with the furylphosphine 8: the ee varied
between 74 % and 89 % for the same series of reactants. The
variation here is not linked to electronic effects in any obvious
way, except for the fact that far better ees are generally
obtained for electron-poor styrenes with catalyst 8 than with
catalyst 2, which makes the former the method of choice in
those cases. The extent of the data obtained with catalyst 8
does not justify a detailed multiparameter analysis;[23] how-
ever, it is worth noting that for p-Me versus m-Me (electron-
releasing case) it is the para isomer that gives the higher ee; in
contrast, for p-Cl versus m-Cl, and for p-CF3 versus m-CF3 ,
the meta isomer gives the higher ee. There is a suggestion of a
weak biphasic trend with higher
ees observed for both electron-
rich and electron-poor substit-
uents.
This leaves the question as to
whether we are seeing a genu-
ine electronic effect in com-
paring PPh2 with P(furyl)2 .[24]
The present consensus is that
trifurylphosphine exerts a net
electron-withdrawing effect on
complexation relative to PPh3 ;
this has been demonstrated
most recently in an electro-
chemical study of the oxidative
addition to Pd0 complexes.[25] Figure 3. Comparison of the conformations of a) tri-2-furylphosphine and b) triphenylphosphine in their iron
The main characteristic of the complexes taken from X-ray structures,[24c] and viewed down the vector of the FeP bond.
Chem. Eur. J. 1999, 5, No. 4  WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999
1320 1330
present results is that the difurylphosphine-based complex 8 is
significantly better with electron-poor vinylarenes; it behaves
as if it were an electron-rich ligand.
The cone angles of furylphosphines and phenylphosphines
are claimed to be quite similar,[24b] although we caution that
the two ligands possess very different M-P-C-C torsion angles
in their complexes. A comparison of the X-ray structures of
the fragments makes this clear (Figure 3).[24c] In addition, a
superficial analysis of the substituent effects may be mislead-
ing in the assessment of electronic effects, since the relative
contribution of conjugative and inductive effects will depend
on the coordination environment. The definitive attempt by
Joerg and Drago[26] to establish a quantitative basis for
P-donors, based on electrostatic and covalent parameters E
and C, recognises this fact; unfortunately, it does not include
data for trifurylphosphine. Although it is not possible to
define in detail, an electronic effect fits nicely with an
empirical model for the enantioselective hydroboration (vide
infra).
A working model for enantioselectivity: The limitations in our
understanding of catalytic hydroboration have been emphas-
ised in the discussion above. The most appropriate starting
point in the development of a model is the C2-symmetrical
BINAP ligand; here the general rule for hydroboration/
oxidation which arose from Hayashis work is that the R
ligand gives the R secondary alcohol. Unfortunately, it is not
possible to extrapolate from the hydrogenation of enamides
catalysed by Rh-BINAP, which is much better understood[27]
and in which the attempted correlation predicts the opposite
enantiomer. Part of the reason may be the differing approach
vectors of H2 and catecholborane in their additions to a
square-planar complex.[28] This approach emphasises that the
overall stereoselectivity is controlled by the configuration of
the reactive RhH, whose transfer to the coordinated
reactant defines the configuration of the new stereogenic
centre. Precedent indicates that the styrene will coordinate in
the P-Rh-P plane with its phenyl anti to the PPh2 group.[29]
Since the same configurational relationship between ligand
and product holds for QUINAP, the pertinent features of this
model hold, with styrene coordinated cis to PPh2 . This places
the borane cis to N, and trans to PPh2 . In a series of square-
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FULL PAPER
planar Pt complexes, electron-rich styrenes coordinate more
strongly trans to pyridine than electron-poor analogues;[30]
hence the trend in enantioselectivity seen in Tables 1 and 2
can be explained by a competition between two pathways (see
Figure 4): the electronic character of the alkene exerts a
Figure 4. A model for the enantioselectivity in the asymmetric hydro-
boration of styrene catalysed by [(S)-QUINAP]Rh and based on X-ray
data for the ligand in its Pd complexes. Structure a) represents intermediate
in the preferred pathway, in which the alkene binds trans to the isoquinoline
nitrogen. This pathway is enantioselective and increasingly favoured as the
styrene is more electron-rich. In the alternative, less enantioselective
pathway via structure structure b), the alkene binds trans to phosphorus; in
both cases the RhH has the same configuration relative to the N-Rh-P
plane.[56]
greater influence on pathway a) than on pathway b); this gives
rise to a higher enantioselectivity when the alkene is electron-
rich. The requirements for a single configuration of RhH
together with endo-alkene coordination (arene away from the
ligand for steric reasons) explain why the symmetrical
substrates acenaphthene and (Z)-stilbene give comparable
ees to other alkenes, and in the same configuration.
The case of catalyst 8 is somewhat different and can be
explained if pathway a) is always more dominant for elec-
tronic reasons. The smaller molar volume and more con-
strained conformation of P(furyl)2 , obvious from the struc-
1326  WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999
J. M. Brown et al.
tural comparison in Figure 3, must be taken into account. This
may permit more access to the exo-coordinated alkene and
hence an overall diminution of the ee. This explanation
predicts that a bulkier ligand with the electronic properties of
the furyl moiety will give superior results. The search is in
progress.
Experimental Section
General: Reactions were conducted with standard vacuum line techniques
under a dry argon atmosphere. Melting points were determined by means
of a Reichert Koffler block. NMR Spectra were recorded on a Varian
Gemini 200 and a Bruker AM 250 or AMX 500 spectrometer. Infrared
spectra were recorded on a Perkin Elmer paragon 1000 spectrometer with
KBr discs. Mass spectra were recorded on a Fison VG platform spectrom-
eter or on a VG BIO Q triple quadrupole mass spectrometer equipped with
a VG electrospray interface. Gas chromatographic analyses were per-
formed on a Fison 8000 with a Chrompack WCOT Fused Silica column, CP-
Chirasil-DEX CB, 25 m; injector temperature: 250 8C; detector tem-
perature: 275 8C; inlet pressure: 2.90 psi. Optical rotations were measured
with a Perkin Elmer 241 spectrometer.
Materials: Reactions were carried out in solvents distilled with standard
drying agents. Catecholborane (Aldrich) was distilled under reduced
pressure before use. 5-Phenyl-5H-dibenzophosphole,[31] 6-[1-(2-hydroxy-
naphthyl)]phenanthridine-trifluoromethanesulfonate,[7] (R)-1-(2-diphenyl-
phosphino-1-naphthyl)isoquinoline,[7] di-m-chloro-bis[ (R)-dimethyl(1-
phenethyl)aminato-C2,N]dipalladium(ii),[32] [Rh(cod)2]BF4 ,[33] [(acac)Rh-
(cod)OSO2CF3],[34] [(Binap)Rh(cod)]BF4 ,[35] 4-dimethylaminostyrene,[36]
2-vinylfuran[37] and 2-vinyl-5-methylfuran[37] were prepared in a manner
similar to the reported procedures.
Preparation of (S)-[1-(2-diphenylphosphino-1-naphthyl)isoquinoline](cy-
clooctadiene)rhodium trifluoromethanesulfonate : (1,5-Cyclooctadi-
ene)(2,4-pentanedionato)rhodium(i) (93 mg, 0.3 mmol) was dissolved in
THF (3 mL) under argon to give a yellow solution.[32] TMS triflate (64 mL,
0.33 mmol) was added from a syringe and the colour darkened slightly. (S)-
1-(2-Diphenylphosphino-1-naphthyl)isoquinoline (132 mg, 0.3 mmol) was
added as a solid with vigorous stirring and the solution turned dark orange
immediately. The solution was stirred for 5 min, reduced in vacuo to 1 mL,
then petrol ether (30 40; 10 mL) was added by syringe to give an orange
solid. The solvent was removed with a syringe and the solid was washed
with petrol ether (30 40; 2  10 mL), then dried in vacuo to give [(S)-1-(2-
diphenylphosphino-1-naphthyl)isoquinoline]rhodium(1,5-cyclooctadiene)
trifluoromethanesulfonate as an orange solid. Yield: 242 mg (100 %); m.p.
135 140 8C; 1H NMR (500 MHz, CDCl3): d 8.92 (d, 3J(H,H) 6.3 Hz,
1 H; H3), 8.26 (d, 3J(H,H) 8.5 Hz, 1 H; H4'), 8.11 (d, 3J(H,H) 8.3 Hz,
1 H; H8'), 7.94 (d, 3J(H,H) 6.3 Hz, 1 H; H4), 7.75 (t, 3J(H,H) 8.2 Hz, 1 H;
H3'), 7.74 (d, 3J(H,H) 8.2 Hz, 1 H; H8), 7.68 (t, 3J(H,H) 7.5 Hz, 1 H;
H7), 7.60 (t, 3J(H,H) 7.2 Hz, 1 H; H7'), 7.56 (td, J 1.7, 7.3 Hz, 1 H; p-
H[A]), 7.49 (td, 3J(H,H) 7.6 Hz, 2J(P,H) 2.4 Hz, 2 H; m-Ph[A]), 7.42 (t,
3
J(H,H) 7.7 Hz, 1 H; H6'), 7.31 (dd, J(H,H) 7.2 Hz, J(P,H) 10.4 Hz, o-
Ph[A]), 7.12 (d, 3J(H,H) 8.4 Hz, 1 H; H5'), 6.88 (d, 3J(H,H) 8.6 Hz, 1 H;
H5), 6.85 6.75 (br m, Ph[B]), 5.40 (br s, 1 H; CH), 5.17 (br s, 1 H; CH),
4.75 (br s, 1 H; CH), 4.00 (br s, 1 H; CH), 3.15 (m, CH2), 2.55 (m, CH2),
2.20 (m, CH2), 1.80 (m, CH2); 13C NMR (62.9 MHz, CDCl3): d 157.1 (d,
J 10 Hz, C1), 143.0 (C3), 140.0 (d, J 15 Hz, C1'), 137 123 (ArC), 103.3
(d, J 12 Hz, CH), 100.5 (d, J 12 Hz, CH), 78.6 (d, J 12 Hz, CH), 76.1
(d, J 12 Hz, CH), 35.6 (s, CH2), 31.6 (s, CH2), 28.5 (s, CH2), 26.4 (s, CH2);
31
P NMR (101.3 MHz, THF): 32.4 (d, J 141 Hz); IR (KBr): nmax 1437
(w) (PPh), 1273 (br s) (SO), 1153 (br m), 1031 (s), 752 (m) (ArH), 702
(m) (ArH), 638 cm1 (s); MS: m/z (electrospray): 650 (100 %) [M].
Preparation of [1-(2-diarylphosphino-1-naphthyl)isoquinoline](cycloocta-
diene)rhodium tetrafluoroborate complexes. General procedure: De-
gassed dichloromethane (5 mL) was added to [Rh(cod)2]BF4 (41 mg,
0.1 mmol) and the 1-(2-diarylphosphino-1-naphthyl)isoquinoline
(0.105 mmol). The mixture was stirred for 20 min and the solvent was then
removed in vacuo. The yellow-orange residue was triturated with diethyl
ether (5 mL). The ether was removed by means of cannula filtration and
the yellow-orange residue dried in vacuo. These complexes are not air
0947-6539/99/0504-1326 $ 17.50+.50/0 Chem. Eur. J. 1999, 5, No. 4
Asymmetric Catalysis
stable and were stored in Schlenk tubes under argon. For the catalytic
hydroboration reactions the complexes were prepared just before use.
[(R)-1-(2-Diphenylphosphino-1-naphthyl)isoquinoline](cyclooctadiene)-
rhodium tetrafluoroborate (2): The reaction of [Rh(cod)2]BF4 (41 mg,
0.1 mmol) and (R)-1-(2-diphenylphosphino-1-naphthyl)isoquinoline
(46 mg, 0.105 mmol)[9] gave 66 mg (90 %) complex 2. This complex is not
air stable and was stored in a Schlenk tube under argon. 1H NMR
(200 MHz, CDCl3): d 8.93 (d, 3J(H,H) 6.3 Hz, 1 H; H3), 8.27 (d,
3
J(H,H) 8.5 Hz, 1 H), 8.12 (d, 3J 8.2 Hz, 1 H), 7.97 (d, 3J(H,H)
6.5 Hz, 1 H), 7.80 6.70 (m), 5.15 (br s, 2 H; cod), 4.75 (br s, 1 H; cod), 3.98
(br s, 1 H; cod), 3.15 (br s, 1 H; cod), 2.55 (br s, 2 H; cod), 2.15 (br s, 1 H; cod),
1.85 (br s, 4 H; cod); 31P NMR (101 MHz, CDCl3): d 32.9 (d, J(P,Rh)
142 Hz); MS (APCI ): m/z: 650 [M].
[ (S)-()-1-(2-Di(3-tolyl)phosphino-1-naphthyl)isoquinoline](cycloocta-
diene)rhodium tetrafluoroborate (4): The same procedure as for complex 2
was followed. Yield: 90 %. This complex is not air stable and was stored in a
Schlenk tube under argon. 1H NMR (200 MHz, CDCl3): d 8.89 (d,
3
J(H,H) 6.3 Hz, 1 H; H3), 8.28 (d, 3J(H,H) 7.7 Hz, 1 H), 8.12 (d, 3J
7.8 Hz, 1 H), 7.99 (d, 3J(H,H) 6.3 Hz, 1 H), 7.85 6.55 (m), 5.17 (br s, 1 H;
cod), 5.03 (br s, 1 H; cod), 4.77 (br s, 1 H; cod), 3.98 (br s, 1 H; cod), 3.12 (br s,
1 H; cod), 2.70 1.70 (br s, 12 H; cod, 2 Me); 31P NMR (101 MHz, CDCl3):
d 32.8 (d, J(P,Rh) 140 Hz); MS (APCI ): m/z: 678.5 [M ].
[(S)-()-1-(2-Di(3,5-xylyl)phosphino-1-naphthyl)isoquinoline](cycloocta-
diene)rhodium tetrafluoroborate (6): The same procedure as for complex 2
was followed. Yield: 92 %. This complex is not air stable and was stored in a
Schlenk tube under argon. 1H NMR (200 MHz, CDCl3): d 8.84 (d,
3
J(H,H) 6.3 Hz, 1 H; H3), 8.30 (d, 3J(H,H) 7.4 Hz, 1 H), 8.13 (d, 3J
7.9 Hz, 1 H), 8.01 (d, 3J(H,H) 6.1 Hz, 1 H), 7.90 6.40 (m), 5.15 (br s, 1 H;
cod), 4.95 (br s, 1 H; cod), 4.82 (br s, 1 H; cod), 4.00 (br s, 1 H; cod), 3.15 (br s,
1 H; cod), 2.57 (br s, 2 H; cod), 2.50 1.70 (m, 17 H; cod, 4Me); 31P NMR
(101 MHz, CDCl3): d 32.1 (d, J(P,Rh) 140 Hz); MS (APCI ): m/z:
706.5 [M].
[ (S )-()-1-(2-Di(2-furyl)phosphino-1-naphthyl)isoquinoline](cycloocta-
diene)rhodium tetrafluoroborate (8): The same procedure as for complex 2
was followed. Yield: 87 %. This complex is not air stable and was stored in a
Schlenk tube under argon. 1H NMR (200 MHz, CDCl3): d 8.90 (d,
3
J(H,H) 6.2 Hz, 1 H; H3), 8.23 (m, 2 H), 8.09 (d, 3J 8.1 Hz, 1 H), 8.03
5.60 (m), 5.30 (br s, 1 H; cod), 5.15 (br s, 1 H; cod), 4.90 (br s, 2 H; cod), 3.15
(br s, 1 H; cod), 2.60 (br s, 2 H; cod), 2.20 (br s, 1 H; cod), 1.90 1.70 (br s, 4 H;
cod); 31P NMR (101 MHz, CDCl3): d 5.4 (d, J(P,Rh) 147 Hz); MS
(APCI ): m/z: 630.3 [M].
[(R)-()-1-(2-Biphenylylenephosphino-1-naphthyl)isoquinoline](cyclooc-
tadiene)rhodium tetrafluoroborate (10): The same procedure as for
complex 2 was followed. Yield: 88 %. This complex is not air stable and
was stored in a Schlenk tube under argon. 1H NMR (200 MHz, CDCl3): d
9.11 (d, 3J(H,H) 6.3 Hz, 1 H; H3), 8.63 (d, 3J(H,H) 6.3 Hz, 1 H), 8.28 (d,
3
J 8.6 Hz, 1 H), 8.10 6.60 (m), 5.38 (br s, 2 H; cod), 4.32 (br s, 1 H; cod),
4.05 (br s, 1 H; cod), 2.80 1.50 (m, 8 H; cod); 31P NMR (101 MHz, CDCl3):
d 29.1 (d, J(P,Rh) 142 Hz); MS (APCI ): m/z: 663.5 [MNH3].
Catalytic hydroboration with catecolborane. General procedure: A sol-
ution of rhodium complex (4 mmol) in dichloromethane was transferred,
strictly under argon, by means of a cannula to a Schlenk tube. The
dichloromethane was evaporated in vacuo, then dry toluene (1 mL), olefin
(0.4 mmol) and freshly distilled catecholborane (0.45 mmol) were added.
The solution was stirred at 20 8C for 2 h, cooled with an ice bath, and
quenched with ethanol (1 mL). NaOH (1 mL, 2 m in H2O) and H2O2 (1 mL,
30 % aqueous) were added, the mixture was allowed to warm up to RT over
30 min and was then stirred for 2 h at this temperature. Et2O (10 mL) was
added to the mixture, and the organic layer was then washed with 1m
aqueous NaOH solution twice and with water once and then dried over
MgSO4 . After evaporation of the solvent, the product was purified by
chromatography on silica (pentane/ether). 1H NMR (200 MHz, CDCl3)
spectra of the products are shown below:
1-(4-Methylphenyl)ethanol: d 7.29 (d, 3J(H,H) 8.2 Hz, 2 H), 7.19 (d,
3
J(H,H) 8.2 Hz, 2 H), 4.86 (q, 3J(H,H) 6.6 Hz, 1 H), 2.36 (s, 3 H), 1.80
(br s, 1 H), 1.48 (d, 3J(H,H) 6.6 Hz, 3 H); [a] 20 D 50 (c 0.5 in chloro-
form) from catalyst 2 [lit.:[5] [a] 20
D 51.6 (c 1 in chloroform) reported for
the R enantiomer (ee: 93.8 %)].
1-(3-Methylphenyl)ethanol: d 7.4 7.0 (m, 4 H), 4.88 (q, 3J(H,H) 6.4 Hz,
1 H), 2.38 (s, 3 H), 1.90 (br s, 1 H), 1.50 (d, 3J(H,H) 6.4 Hz, 3 H); [a] 20
D enantiomer (ee: 98.7 %)].
Chem. Eur. J. 1999, 5, No. 4  WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999
1320 1330
29 (c 0.5 in chloroform) from catalyst 2 [lit.:[38] [a] 21
D 40.4 (c 0.53
in ethanol) reported for the R enantiomer].
1-(2-Methylphenyl)ethanol: d 7.6 7.1 (m, 4 H), 5.13 (q, 3J(H,H) 6.4 Hz,
1 H), 2.35 (s, 3 H), 1.70 (br s, 1 H), 1.47 (d, 3J(H,H) 6.4 Hz, 3 H); [a] 20 D
31.2 (c 0.5 in chloroform) from catalyst 2 [lit.:[36] [a] 16
D 70 (c 0.34 in
ethanol) reported for the R enantiomer].
1-(2,4-Dimethylphenyl)ethanol: d 7.5 7.0 (m, 3 H), 5.11 (q, 3J(H,H)
6.4 Hz, 1 H), 2.32 (s, 6 H), 1.70 (br s, 1 H), 1.47 (d, 3J(H,H) 6.4 Hz, 3 H);
[a] 20
D 51.2 (c 0.5 in chloroform) from catalyst 2 [lit.: [a] 28
D 46.3
[42]
(c 1.57 in methanol), configuration unassigned but R by analogy with
other results in this paper].
1-(2,4,6-Trimethylphenyl)ethanol: d 6.80 (s, 2 H), 5.35 (q, 3J(H,H)
6.7 Hz, 1 H), 2.40 (s, 6 H), 2.24 (s, 3 H), 1.70 (br s, 1 H), 1.50 (d, 3J(H,H)
D 37.3 (c 0.5 in chloroform) from catalyst 2 [lit.:
6.8 Hz, 3 H); [a] 20 [39]
[a] 20
D 52.5 (c 1.1 in chloroform) reported for the R enantiomer].
2-(2,4,6-Trimethylphenyl)ethanol: d 6.84 (s, 2 H), 3.73 (t, 3J(H,H)
7.5 Hz, 2 H), 2.92 (t, 3J(H,H) 7.5 Hz, 2 H), 2.33 (s, 6 H), 2.28 (s, 3 H), 1.60
(br s, 1 H).
1-(4-Dimethylaminophenyl)ethanol: d 7.30 (d, 3J(H,H) 8.8 Hz, 2 H),
6.70 (d, 3J(H,H) 8.8 Hz, 2 H), 4.78 (q, 3J(H,H) 6.5 Hz, 1 H), 2.98 (s, 6 H),
1.75 (br s, 1 H), 1.51 (d, 3J(H,H) 6.5 Hz, 3 H); [a] 20D 16.4 (c 0.5 in
chloroform) from catalyst 8 [lit.:[40] [a] 23
D 52 (c 1 in MeOH) reported
for the R enantiomer].
1-(4-Methoxyphenyl)ethanol: d 7.31 (d, 3J(H,H) 8.6 Hz, 2 H), 6.90 (d,
3
J(H,H) 8.6 Hz, 2 H), 4.87 (t, 3J(H,H) 6.5 Hz, 1 H), 3.82 (s, 3 H), 1.74
(br s, 1 H), 1.48 (d, 3 H), [a] 22D 39.6 (c 0.5 in chloroform, 75 % ee
[41]
)
[lit.:[5] [a] 23
D 45.2 (c 1.01 in chloroform) reported for the R enantiom-
er].
1-(4-Ethoxyphenyl)ethanol: d 7.30 (d, 3J(H,H) 8.8 Hz, 2 H), 6.87 (d,
3
J(H,H) 8.8 Hz, 2 H), 4.85 (q, 3J(H,H) 6.4 Hz, 1 H), 4.02 (q, 3J(H,H)
7.0 Hz, 2 H), 1.80 (br s, 1 H), 1.47 (d, 3J(H,H) 6.4 Hz, 3 H), 1.40 (t,
3
J(H,H) 8.0 Hz, 3 H); [a] 20
D 46 (c 0.5 in chloroform) from (R)-
Quinap.
1-(4-Fluorophenyl)ethanol: d 7.4 7.1 (m, 4 H), 4.86 (q, 3J(H,H) 6.4 Hz,
1 H), 1.90 (br s, 1 H), 1.48 (d, 3J(H,H) 6.4 Hz, 3 H); [a] 20
D 24 (c 0.5 in
chloroform) from catalyst 2 [lit.:[42] [a] 20
D 40.2 (c 1.2 in chloroform)
reported for the R enantiomer (ee > 97 %)].
1-(3-Fluorophenyl)ethanol: d 7.4 6.8 (m, 4 H), 4.87 (q, 3J(H,H) 6.4 Hz,
1 H), 1.90 (br s, 1 H), 1.48 (d, 3J(H,H) 6.4 Hz, 3 H); [a] 20
D 16.4 (c 0.5
in chloroform) from catalyst 8 [lit.:[43] [a] 25
D 38.5 (c 1.2 in MeOH)].
1-(2-Fluorophenyl)ethanol: d 7.6 6.8 (m, 4 H), 5.20 (q, 3J(H,H) 6.6 Hz,
1 H), 2.00 (br s, 1 H), 1.51 (d, 3J(H,H) 6.6 Hz, 3 H); [a] 20
D 16.8 (c 0.5
in chloroform) from catalyst 8 [lit.:[44] [a] 20
D 45.4 (c 1.4 in CHCl3) for
the R enantiomer].
1-(2,6-Difluorophenyl)ethanol: d 7.3 6.6 (m, 4 H), 5.27 (q, 3J(H,H)
6.6 Hz, 1 H), 2.10 (br s, 1 H), 1.64 (d, 3J(H,H) 6.6 Hz, 3 H); [a] 20
D 5.8
(c 0.5 in chloroform) from catalyst 8.
1-(4-Chlorophenyl)ethanol: d 7.4 7.1 (m, 4 H), 4.85 (q, 3J(H,H) 6.6 Hz,
1 H), 1.70 (br s, 1 H), 1.47 (d, 3J(H,H) 6.6 Hz, 3 H); [a] 20
D 36 (c 0.5 in
chloroform) from catalyst 8 [lit.:[45] [a] 20
D 48.8 (c 3.13 in chloroform)
reported for the S enantiomer (ee: 99 %)].
1-(3-Chlorophenyl)ethanol: d 7.4 7.1 (m, 4 H), 4.85 (q, 3J(H,H) 6.6 Hz,
1 H), 1.70 (br s, 1 H), 1.47 (d, 3J(H,H) 6.6 Hz, 3 H); [a] 20
D 32.8 (c 0.5
in chloroform) from catalyst 8 [lit.:[5] [a] 20
D 36.7 (c 1 in chloroform)
reported for the R enantiomer (ee: 84.6 %)].
1-(2-Chlorophenyl)ethanol: d 7.4 7.1 (m, 4 H), 5.31 (q, 3J(H,H) 6.6 Hz,
1 H), 1.80 (br s, 1 H), 1.48 (d, 3J(H,H) 6.6 Hz, 3 H); [a] 20
D 21.2 (c 0.5
in chloroform) from catalyst 8 [lit.:[5] [a] 20
D 22.4 (c 1.1 in chloroform)
reported for the R enantiomer (ee: 72.1 %)].
1-(2,6-Dichlorophenyl)ethanol: d 7.4 7.1 (m, 3 H), 5.58 (dq, 3J(H,H)
10.4 and 6.9 Hz, 1 H), 3.12 (d, 3J(H,H) 10.4 Hz, 1 H), 1.67 (d, 3J(H,H)
D 3.4 (c 1 in chloroform) from catalyst 2.
6.9 Hz, 3 H); [a] 20
1-(4-Trifluoromethylphenyl)ethanol : d 7.7 7.4 (m, 4 H), 4.97 (q,
3
J(H,H) 6.5 Hz, 1 H), 1.80 (br s, 1 H), 1.51 (d, 3J(H,H) 6.5 Hz, 3 H);
[a] 20
D 16.4 (c 0.5 in chloroform) and 18.5 (c 0.2 in methanol) from
catalyst 8 [lit.:[46] [a] 20
D 29.8 (c 1.088 in methanol) reported for the R
0947-6539/99/0504-1327 $ 17.50+.50/0 1327
FULL PAPER J. M. Brown et al.

1-(3-Trifluoromethylphenyl)ethanol : d 7.7 7.4 (m, 4 H), 4.98 (q, 4-Chromanol: d 7.4 6.7 (m, 4 H), 4.80 (t, 3J(H,H) 3.4 Hz, 1 H), 4.28 (m,
3
J(H,H) 6.4 Hz, 1 H), 1.80 (br s, 1 H), 1.53 (d, 3J(H,H) 6.4 Hz, 3 H); D 44 (c 1 in chloroform) and
2 H), 2.10 (m, 2 H), 1.80 (br s, 1 H); [a] 20
D 21.4 (c 1 in chloroform) from catalyst 8 [lit.:
[a] 20 [47]
[a] 22
D 28 (c 51 (c 1 in ethanol) from catalyst 2 [lit.:[54] [a] 20 D 67 (c 0.5 in
0.78 in methanol) reported for the R enantiomer]. ethanol) reported for the R enantiomer (ee: 98 %)].
1-(2-Trifluoromethylphenyl)ethanol : d 7.9 7.2 (m, 4 H), 5.33 (q, Determination of enantiomeric excesses and absolute configuration
3
J(H,H) 6.4 Hz, 1 H), 2.10 (br s, 1 H), 1.50 (d, 3J(H,H) 6.4 Hz, 3 H); Method A: By NMR with [Eu(hfc)3] as a chiral shift reagent; absolute
D 15.8 (c 0.5 in chloroform) from catalyst 8, [lit.:
[a] 20 [42]
[a] 22
D 29.2 configuration determined by comparison of the sign of optical rotation with
(c 0.795 in methanol) reported for the R enantiomer, 62 % ee]. the literature, unless otherwise stated.
1-[3,5-Bis(trifluoromethyl)phenyl]ethanol: d 7.82 (s, 2 H), 7.70 (s, 1 H), 1-(4-Dimethylaminophenyl)ethanol: ee calculated on CHMe shifted to d
5.03 (q, 3J(H,H) 6.6 Hz, 1 H), 2.10 (br s, 1 H), 1.53 (d, 3J(H,H) 6.6 Hz, 9 10. (S)-() enantiomer was obtained from catalyst 8.
3 H); [a] 20
D 13.2 (c 0.5 in chloroform) from catalyst 8 [lit.:
[48]
[a] 20
D 1-(2-methoxy-1-naphthyl)ethanol: ee calculated on an aromatic proton
21 (c 1, MeOH) reported for the R enantiomer, 94 % ee]. shifted to d 9-10, absolute configuration assumed by analogy.
1-(9-anthryl)ethanol: ee calculated on an aromatic proton shifted to d 9
1-(2-Naphthyl)ethanol: d 7.9 7.6 (m, 5 H), 7.5 7.3 (m, 3 H), 4.95 (q,
10. (R)-() enantiomer was obtained from catalyst (R)-2.
3
J(H,H) 6.8, 1 H), 2.40 (br s, 1 H), 1.50 (d, 3J(H,H) 6.8 Hz, 3 H).
1-ferrocenylethanol: ee calculated on CHMe shifted to d 6 7. (S)-()
1-(1-Naphthyl)ethanol: d 8.12 (d, 3J(H,H) 8.6, 1 H), 7.80 (d, 3J(H,H) enantiomer was obtained from catalyst 8.
8.2, 1 H), 7.78 (d, 3J(H,H) 9.0, 1 H), 7.49 (t, 3J(H,H) 8.3, 1 H), 7.36 (t, 1,2-diphenylethanol: ee calculated on an ortho-aromatic proton shifted to
3
J(H,H) 8.4, 1 H), 7.27 (d, 3J(H,H) 9.0, 1 H), 5.76 (q, 3J(H,H) 6.8, 1 H), d 10 11. (R)-( ) enantiomer was obtained from (R)-Quinap.
2.05 (br s, 1 H), 1.68 (d, 3J(H,H) 6.8 Hz, 3 H); [a] 23 D 23.3 (c 2.0 in 1-acenaphthenol: ee calculated on an aromatic proton shifted to d 9 10.
ethanol) from catalyst 2 [lit.:[42] [a] 28D 66.7 (c 0.31 in methanol) (R)-() enantiomer was obtained from catalyst (R)-2.
reported for the R enantiomer]. 4-chromanol: ee calculated on an aromatic proton shifted to d 10 11.
1-(2-Methoxy-(1)-naphthyl)ethanol: d 8.12 (d, 3J(H,H) 8.6, 1 H), 7.80 The (R)-() enantiomer was obtained from (R)-2.
(d, 3J(H,H) 8.2, 1 H), 7.78 (d, 3J(H,H) 9.0, 1 H), 7.49 (t, 3J(H,H) 8.3, Method B: By gas chromatography with a Chrompack WCOT Fused Silica
1 H), 7.36 (t, 3J(H,H) 8.4, 1 H), 7.27 (d, 3J(H,H) 9.0, 1 H), 5.76 (q, column, CP-Chirasil-DEX CB, 25 m; inlet pressure: 2.90 psi (Table 5).
3
J(H,H) 6.8, 1 H), 3.99 (s, 3 H), 2.05 (br s, 1 H), 1.68 (d, 3J(H,H) 6.8 Hz, Catalytic hydroboration of styrene: Styrene (0.86 mL, 7.5 mmol) was added
3 H); 13C NMR: d 154.5, 129.5, 129.3, 128.8, 126.8, 125.7, 123.8, 122.9, to a solution of catalyst [(S)-2]OTf (0.012 g, 15 mmol, 0.2 mol %) in THF
117.0, 113.5 (Ar) 66.1 (CH), 56.3 (OCH3)), 23.7 ((CH3); MS (APCI): m/z: (5 mL) under argon. The solution was stirred for 5 min and freshly distilled
186 (39 %) 185 (100 %); IR (KBr): n 3307, 1249, 1056 cm1; [a] 22 D 9.45 catecholborane (0.80 mL, 7.5 mmol) was then added. The mixture was
(c 0.92 in chloroform) from catalyst 2. stirred at ambient temperature for 8 h and then quenched with EtOH
1-(9-Anthryl)ethanol: d 8.7 8.5 (m, 2 H), 8.3 (s, 1 H), 8.1 7.8 (m, 2 H), (2 mL). NaOH (2 m, 10 mL) and H2O2 (1 mL) were added and the mixture
7.6 7.3 (m, 4 H), 6.35 (q, 3J(H,H) 6.3, 1 H), 2.10 (br s, 1 H), 1.85 (d, was stirred for 2 h. The reaction mixture was extracted into Et2O, washed
3
J(H,H) 6.3 Hz, 3 H), [a] 22 D 11.47 (c 0.91 in tetrahydrofuran) from (2 m NaOH, H2O, brine) dried over MgSO4 , and the product isolated by
catalyst 2 [lit.:[49] [a] 20
D 15.7 (0.7 in tetrahydrofuran) reported for the R chromatography on Florosil (Et2O/pentane 1:1). This gave (S)-1-phenyl-
enantiomer]. ethanol [0.647 g (71 %, 99 % secondary isomer, 91 % ee by GC as described
2-Furylethanol: d 7.40 (d, 3J(H,H) 1.0 Hz, 1 H), 6.38 (m, 1 H), 6.27 (d, D 50.2 (c 1 in chloroform) [lit:
above)]; [a] 23 [55]
[a] 23
D 54.0 (c 5.1 in
3
J(H,H) 2.7 Hz, 1 H), 4.89 (q, 3J(H,H) 6.6 Hz, 1 H), 1.90 (br s, 1 H), 1.55 chloroform) reported for the (S)-enantiomer].
(d, 3J(H,H) 6.6 Hz, 3 H); [a] 20 D 9.6 (c 0.5 in chloroform) from
Catalytic hydroboration of 1,2-dihydronaphthalene: A solution of catalyst
catalyst 8 [lit.:[50] [a] 20
D 20.8 (c 1.3 in chloroform) reported for the R
[(R)-2]BF4 (8 mmol) in dichloromethane was transferred by means of a
enantiomer (ee: 95 %)]. cannula to a Schlenk tube, strictly under argon. The dichloromethane was
evaporated in a vacuum then dry toluene (10 mL), 1,2-dihydronaphthalene
2-(5-Methylfuryl)ethanol: d 6.11 (d, 3J(H,H) 2.6 Hz, 1 H), 5.91 (d,
(520 mg, 4 mmol) and freshly distilled catecholborane (600 mg, 5 mmol)
3
J(H,H) 2.6 Hz, 1 H), 4.84 (q, 3J(H,H) 6.6 Hz, 1 H), 2.30 (s, 3 H), 1.70
were added. The solution was stirred at 20 8C for 24 h, cooled in an ice bath
(br s, 1 H), 1.53 (d, 3J(H,H) 6.6 Hz, 3 H); [a] 20D 8.4 (c 0.5 in chloro-
and quenched with EtOH (5 mL). After the addition of NaOH (5 mL, 2 m
form) from catalyst 8 [lit.:[51] [a] 20
D 8.5 (c 2.2 in chloroform) reported
in H2O) and H2O2 (5 mL., 30 % aqueous), the mixture was allowed to warm
for the R enantiomer (ee: 95 %)].
to RT over 30 min and was then stirred for 2 h at this temperature. Ether
1-Ferrocenylethanol: d 4.53 (q, 3J(H,H) 6.5 Hz, 1 H), 4.3 4.0 (m, 9 H), (20 mL.) was added to the mixture then the aqueous layer was extracted
1.80 (br s, 1 H), 1.45 (d, 3J(H,H) 6.5 Hz, 3 H); [a] 20D 23.6 (c 0.5 in with two portions of dichloromethane (20 mL.) The organic layers were
chloroform) and [a] 20 D 21.4 (c 0.5 in benzene) from catalyst 2 [lit.:
[52]
dried over MgSO4 . After evaporation of the solvents, the product was
[a] 25
D 29.3 (c 1.7 in benzene) reported for the S enantiomer]. purified by chromatography on silica (pentane/ether) to afford 0.564g
1-Phenylpropanol: d 7.5 7.2 (m, 5 H), 4.55 (t, 3J(H,H) 6.7 Hz, 1 H), (95 %) of (R)-1,2,3,4-tetrahydro-1-naphthol (ee: 96.2 % by GC).
2.23 (br s, 1 H), 1.90 1.50 (m, 2 H), 0.88 (d, 3J(H,H) 6.7 Hz, 3 H).
1,2-Diphenylethanol: d 7.4 7.1 (m, 10 H), 4.90 (dd, 3J(H,H) 8.0 and
5.4 Hz, 1 H), 3.2 2.9 (m, 2 H), 1.8 (br s, 1 H); [a] 20
D 34 (c 0.5 in
chloroform) from catalyst 2 [lit.:[53] [a] 20
Acknowledgements
D 8.5 (c 5 in chloroform)
reported for the R enantiomer].
We thank EPSRC, DTI and Chiroscience (Dr. U. Berens), Glaxo Well-
1-(4-Methoxyphenyl)propanol: d 7.28 (d, 3J(H,H) 8.8 Hz, 2 H), 6.90 (d,
come (Dr. A. Payne), Robinson Bros.(Dr. K. Soares), SB (Dr. P. Sheldrake)
3
J(H,H) 8.8 Hz, 2 H), 4.56 (t, 3J(H,H) 6.7 Hz, 1 H), 3.82 (s, 3 H), 1.90
and Zeneca FCMO (Dr. A. J. Blacker) for support under the LINK
1.70 (m, 2 H), 0.91 (t, 3J(H,H) 6.7 Hz, 3 H); [a] 20 D 29 (c 0.5 in
Asymmetric Synthesis Programme. We thank the Spanish Government for
chloroform) and 26.4 (c 0.5 in benzene) from catalyst 2 [lit.:[54] [a] 20
D
a Scholarship (EF). Johnson Matthey kindly provided a loan of RhCl3
36 (c 1 in chloroform) reported for the R enantiomer (ee: 99 %)].
3 H2O.
1-Indanol: d 7.5 7.1 (m, 4 H), 5.19 (t, 3J(H,H) 6.1 Hz, 1 H), 3.2 2.3 (m,
3 H), 2.10 (br s, 1 H), 2.0 1.8 (m, 1 H).
1-Acenaphthenol: d 7.8 7.3 (m, 6 H), 5.72 (dd, 3J(H,H) 7.1 and 2.5 Hz, [1] H. Kono, K. Ito, Y. Nagai, Chemistry Lett. 1976, 1095 1098.
1 H), 3.81 (dd, 2J(H,H) 17.8 and 3J(H,H) 7.1 Hz, 1 H), 3.23 (dd, [2] J. D. Hewes, C. W. Kriemendahl, T. B. Marder, M. F. Hawthorne, J.
2
J(H,H) 17.8 and 3J(H,H) 2.5 Hz, 1 H); [a] 23 D 1.62 (c 1.23 in Am. Chem. Soc. 1984, 106, 5757 5759, and earlier papers in this
chloroform) from (R)-Quinap [lit.:[18] [a]D 1.46 (c 1.23 in chloroform) series.
reported for the R enantiomer]. [3] D. Mannig, H. Noth, Angew. Chem. 1985, 97 979 980; Angew. Chem.
1,2,3,4-Tetrahydro-1-naphthol: d 7.5 7.1 (m, 4 H), 4.80 (t, 3J(H,H) Int. Ed. Engl. 1985, 24, 878 879.
4.3 Hz, 1 H), 3.1 2.7 (m, 2 H), 2.1 1.7 (m, 5 H). [4] K. Burgess, M. J. Ohlmeyer, J. Org. Chem. 1988, 53, 5178 5179.

1328  WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 0947-6539/99/0504-1328 $ 17.50+.50/0 Chem. Eur. J. 1999, 5, No. 4
Asymmetric Catalysis 1320 1330

Table 5. Determination of enantiomeric exesses and absolute configuration by GC.

a-Aryl alcohol Temperature Retention Time [min]
of oven [8C] Enantiomer 1 Enantiomer 2 b-Aryl alcohol
(4-methylphenyl)ethanol 125 19.8 (R)-() [a]
21.6 (S)-() 23.3
(3-methylphenyl)ethanol 105 61.0 (R)-()[a] 65.8 (S)-() 63.6
(2-methylphenyl)ethanol 125 27.1 (R)-()[a] 33.0 (S)-() 31.2
(2,4-dimethylphenyl)ethanol 130 30.3 (R)-()[b] 38.1 (S)-() 35.6
(2,4,6-trimethylphenyl)ethanol 140 37.4 (R)-()[a] 47.7 (S)-() 41.6
(4-methoxyphenyl)ethanol 110 65.0 (R)-()[a] 75.8 (S)-()
(4-ethoxyphenyl)ethanol 135 37.4 (R)-()[b] 39.7 (S)-() 47.2
(4-fluorophenyl)ethanol 120 20.9 (R)-()[a] 23.1 (S)-() 26.6
(3-fluorophenyl)ethanol 120 21.3 (R)-()[a] 24.0 (S)-() 25.3
(2-fluorophenyl)ethanol 120 19.0 (R)-()[a] 20.3 (S)-() 21.8
(2,6-difluorophenyl)ethanol 110 18.7 (R)-()[b] 20.1 (S)-() 31.4
(4-chlorophenyl)ethanol 130 35.9 (R)-()[a] 39.9 (S)-() 46.2
(3-chlorophenyl)ethanol 130 35.9 (R)-()[a] 39.0 (S)-() 41.8
(2-chlorophenyl)ethanol 130 33.2 (R)-()[a] 41.6 (S)-() 36.7
(2,6-dichlorophenyl)ethanol 140 32.3 (R)-()[c] 38.0 (S)-() 53.2
(4-trifluoromethylphenyl)ethanol 130 17.5 (R)-()[a] 19.5 (S)-() 22.5
(3-trifluoromethylphenyl)ethanol 130 14.0 (R)-()[a] 15.3 (S)-() 16.5
(2-trifluoromethylphenyl)ethanol 120 19.8 (R)-()[a] 21.5 (S)-() 24.8
(3,5-bistrifluoromethylphenyl)ethanol 120 14.5 (R)-()[a] 16.2 (S)-() 19.1
(2-naphthyl)ethanol 150[e] 35.6 (R)-()[d] 38.4 (S)-()
(1-naphthyl)ethanol 150 66.6 (S)-()[d] 71.7 (R)-() 78.8
2-furylethanol 80 35.7 (R)-()[a] 37.3 (S)-() 46.6
2-(5-methylfuryl)ethanol 80 62.4 (R)-()[a] 63.7 (S)-() 69.5
1-phenylpropanol 120 41.6 (R)-()[d] 42.5 (S)-()
1-phenyl-3-(trimethysilyloxy)propanol 130[f] 152.2 159.3
(4-methoxyphenyl)propanol 130 55.2 (R)-()[a] 60.1 (S)-()
1-indanol 105 88.0 (S)-()[d] 91.0 (R)-()
1,2,3,4-tetrahydro-1-naphthol 130 48.7 (S)-()[d] 49.7 (R)-()

[a] Absolute configuration determined by comparison of the sign of optical rotation with the literature. [b] Absolute configuration assigned by similarity in
the order of elution in the GC analysis and from the sign of optical rotation. [c] Absolute configuration assigned by similarity in the order of elution in the GC
analysis. [d] Absolute configuration determined by comparison with an authentic sample (Aldrich). [e] Inlet pressure: 6.7 psi. [f] SGE column; inlet pressure:
14 psi.

[5] T. Hayashi, Y. Matsumoto, Y. Ito, Tetrahedron: Asymmetry 1991, 2,
601 612.
[6] A. Schnyder, L. Hintermann, A. Togni, Angew. Chem. 1995, 107 996
998; Angew. Chem. Int. Ed. Engl. 1995, 34, 931 933; A. Schnyder, A.
Togni, U. Wiesli, Organometallics 1997, 16, 255 260.
[7] J. M. Brown, D. I. Hulmes, T. P. Layzell, J. Chem. Soc. Chem.
Commun. 1993, 1673 1674; J. M. Valk, G. A. Whitlock, T. P. Layzell,
J. M. Brown, Tetrahedron: Asymmetry 1995, 6, 2593 2596.
[8] I. Beletskaya, A. Pelter, Tetrahedron 1997, 53, 4957 5026; for earlier
work see: K. Burgess, M. J. Ohlmeyer, Chem. Rev. 1991, 91, 1179 1191.
[9] N. W. Alcock, J. M. Brown, D. I. Hulmes, Tetrahedron: Asymmetry
1993, 4, 743 756.
[10] H. Doucet, J. M. Brown, Tetrahedron: Asymmetry 1997, 8, 3775 3784.
[11] E. Fernandez, M. W. Hooper, F. I. Knight, J. M. Brown, Chem.
Commun. 1997, 173 174.
[12] F. I. Knight, J. M. Brown, D. Lazzari, A. Ricci, A. J. Blacker,
Tetrahedron 1997, 53, 11 411 11 424.
[13] S. A. Westcott, H. P. Blom, T. B. Marder, R. T. Baker, J. C. Calabrese,
Inorg. Chem. 1993, 32, 2175 2182.
[14] J. M. Brown, G. C. Lloyd-Jones, J. Am. Chem. Soc. 1994, 116, 866
878.
[15] W. Huckel, F. Mossner, Liebigs Ann. Chem. 1960, 637, 57 72.
[16] J. Jacques, A. Collet, S. H. Wilen, Enantiomers, Racemates and
Resolutions, Kreiger, Malabar, Florida, 1991.
[17] H. Kwart, D. P. Hoster, J. Org. Chem. 1967, 32, 1867 1870; D. L.
Garin, D. J. C. Grieco, L. Kelly, J. Org. Chem. 1977, 42, 1249 1251;
L. A. Paquette, C. J. Lau, J. Org. Chem. 1987, 52, 1634 1635; M.
Farina, G. Disilvestro, Mol. Cryst. Liq. Cryst. 1988, 161, 177 198.
[18] Y. Hu, H. Ziffre, J. V. Silverton, Can. J. Chem. 1989, 67, 60 62.
[19] D. A. Evans, G. C. Fu, B. A. Anderson, J. Am. Chem. Soc. 1992, 114,
6679 6685; K. Burgess, W. A. Van der Donk, S. A. Westcott, T. B.
Marder, R. T. Baker, J. C. Calabrese, J. Am. Chem. Soc. 1992, 114,
9350 9393; S. A. Westcott, H. P. Blom, T. B. Marder, R. T. Baker, J.
Am. Chem. Soc. 1992, 114, 8863 8869.
[20] H. Werner, M. Schafer, O. Nurnberg, J. Wolf, Chem. Ber. 1994, 127,
27 38; B. Ebbinghaus, M. T. Madigan, C. E. Osterberg, L. C. Nathan,
Acta Crystallogr. C 1988, 44, 21 23; S. D. Chappell, D. J. Cole-
Hamilton, A. Galas, M. B. Hursthouse, N. Walker, Polyhedron 1985, 4,
121 125.
[21] A. E. Dorigo, P. von R. Schleyer, Angew. Chem. 1995, 107 108 111;
Angew. Chem. Int. Ed. Engl. 1995, 34, 115 118; D. G. Musaev, K.
Morokuma, J. Phys. Chem. 1996, 100, 6509 6517.
[22] Dr. T. P. Layzell, unpublished results; for the ligand synthesis see: J.
Sprinz, G. Helmchen, Tetrahedron Lett. 1993, 34, 1769 1772; P.
von Matt , A. Pfaltz, Angew. Chem. 1993, 105 614 617; Angew. Chem.
Int. Ed. Engl. 1993, 32, 566 568; G. J. Dawson, C. G. Frost, J.
Williams, Tetrahedron Lett. 1993, 34, 3149 3150.
[23] R. D. Topsom, Prog. Phys Org. Chem. 1987, 16, 125 235.
[24] a) D. W. Allen, B. F. Taylor, J. Chem. Soc. Dalton Trans. 1982, 51 54;
b) M. Ogasawara, F. Maseras, N. Gallego-Planas, K. Kawamura, K.
Ito, K. Toyota, W. E. Streib, S. Komiya, O. Eisenstein, K. G. Caulton,
Organometallics 1997, 16, 1979 1993; c) X-ray structure of [(fur-
yl)3PFe]: C. Santelli-Rouvier, C. Coin, L. Toupet, M. Santelli, J.
Organomet. Chem. 1995, 495, 91 96; X-ray structure of [Ph3PFe]:
P. E. Riley, R. E. Davis, Inorg. Chem. 1980, 19, 159 165.
[25] C. Amatore, A. Jutand, G. Meyer, H. Atmani, F. Khalil, F. O. Chahdi,
Organometallics 1998, 17, 2958 2964.
[26] R. S. Drago, S. Joerg, J. Am. Chem. Soc. 1996, 118, 2654 2663; S.
Joerg, R. S. Drago, J. Sales, Organometallics 1998, 17, 589 599.
[27] T. Ikariya, Y. Ishii, H. Kawano, T. Arai, M. Saburi, S. Yoshikawa, S.
Akutagawa, J. Chem. Soc. Chem. Commun. 1985, 922 924.
[28] B. P. Cleary, R. Eisenberg, Organometallics 1995, 14, 4525 4534.
[29] K. Miki, O. Shiotani, Y. Kai, N. Kasai, H. Kanatani, H. Kurosawa,
Organometallics 1983, 2, 585 593; for an overview of metal alkene

Chem. Eur. J. 1999, 5, No. 4  WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 0947-6539/99/0504-1329 $ 17.50+.50/0 1329
FULL PAPER J. M. Brown et al.

binding see: J. A. Gladysz, B. J. Boone, Angew. Chem. 1997, 109, 566 [43] K. Naemura, M. Murata, R. Tanaka, M. Yano, K. Hirose, Y. Tobe,
602; Angew. Chem. Int. Ed. Engl. 1997, 36, 551 583. Tetrahedron: Asymmetry, 1996, 7, 3285 3294.
[30] H. Kurosawa, I. Ikeda, J. Organomet. Chem. 1992, 428, 289 301. [44] C. Meier, W. H. G. Laux, Tetrahedron 1996, 52, 589 598.
[31] S. Ogawa, Y. Tajiri, N. Furukawa, Bull. Chem. Soc. Jpn. 1991, 64, [45] Y. Akakabe, M. Takahashi, M. Kamezawa, K. Kikuchi, H. Tachibana,
3182 3184. T. Ohtani, Y. Naoshima, J. Chem. Soc. Perkin Trans. 1995, 1295 1298.
[32] D. G. Allen, G. M. McLaughlin, G. B. Robertson, W. L. Steffen, G. [46] D. J. Mathre, A. S. Thompson, A. W. Douglas, K. Hoogsteen, J. D.
Salem, S. B. Wild, Inorg. Chem. 1982, 21, 1007; H. T. Clarke, H. B. Carrol, E. G. Corley, E. J. J. Grabowski, J. Org. Chem. 1993, 58, 2880
Gillespie, S. Z. Weisshaus, J. Am. Chem. Soc. 1933, 55, 4571 87. 2888.
[33] M. D. Fryzuk, B. Bosnich, J. Am. Chem. Soc. 1977, 99, 6262 6267. [47] K. Naemura, R. Fukada, M. Murata, M. Konishi, K. Hirose, Y. Tobe,
[34] J. M. Brown, P. L. Evans, A. P. James, Organic Syntheses 1989, 68, 64 Tetrahedron: Asymmetry 1995, 6, 2385 2394.
76. [48] S. T. Pickard, H. E. Smith, J. Am. Chem. Soc 1990, 112, 5741 5747.
[35] K. Tani, T. Akutagawa, H. Kumobayashi, T. Taketomi, H. Takaya, A. [49] K. Okada, H. Sakai, M. Oda, A. Yoshimura, T. Ohno, Tetrahedron
Miyashita, R. Noyori, S. Otsuka, J. Am. Chem. Soc. 1984, 106, 5208 Lett. 1989, 30, 1091 1094.
17. [50] M. Kusakabe, Y. Kitano, Y. Koboyashi, F. Sato, J. Org. Chem. 1989, 54,
[36] R. W. Strassburg, R. A. Gregg, C. Walling, J. Am. Chem. Soc. 1947, 69, 2085 2091.
2141 2143. [51] G. Fantin, M. Fogagnolo, A. Medici, P. Pedrini, S. Poli, F. Gardini,
[37] I. V. Andreeva, M. M. Koton, Dokl. Akad. Nauk. SSSR, 1956, 110, Tetrahedron: Asymmetry. 1993, 4, 1607 1612.
75 78. [52] G. W. Gokel, D. Marquarding, I. K. Ugi, J. Org. Chem. 1972, 37, 3052
[38] K. Nakamura, M. Kawasaki, A. Ohno, Bull. Chem. Soc. Japan, 1996, 3058.
69, 1079 1085. [53] W.Gerrard, M. Kenyon, J. Chem. Soc. 1928, 2564 2567.
[39] M. Kasai, C. Froussios, H. Ziffer, J. Org. Chem. 1983, 48, 459 [54] T. Shono, N. Kise, E. Shirakawa, H. Matsumoto, E. Okazaki, J. Org.
464. Chem. 1991, 56, 3063 3067.
[40] S. Hashiguchi, A. Fujii, K. J. Haack, K. Matsumura, T. Ikariya, R. [55] H. L. Holland, T. S. Manoharan, F. Schweizer, Tetrahedron: Asym-
Noyori, Angew. Chem. 1997, 109, 300 303; Angew. Chem. Int. Ed. metry 1991, 2, 335 338.
Engl. 1997, 36, 288 290. [56] J. M. Brown, S. W. Leppard, G. C. Lloyd-Jones, Tetrahedron: Asym-
[41] G. Lloyd-Jones, D. Phil thesis, Oxford, 1992. metry 1992, 3, 261 66.
[42] T. R. Nieduzak, A. L. Margolin, Tetrahedron: Asymmetry 1991, 2,
113 122. Received: September 1, 1998 [F 1384]

1330  WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999 0947-6539/99/0504-1330 $ 17.50+.50/0 Chem. Eur. J. 1999, 5, No. 4