SYNLETT

2897
P. R. Krishna* R. Sachwani P. S. Reddy
O * R1CHO + R2O

Accounts and Rapid Communications in Synthetic Organic Chemistry

2008 No. 19 December I

EWG R1CHO +

intramolecular

chiral electrophiles
OH R1 * EWG

O + * OR2

chiral acrylates R1CHO chiral base

O R1CHO +

double asymmetric induction

* OR2

EWG EWG = CO2Et, CN, COMe R1CHO +

2913

J. P. Wolfe*

Stereoselective Synthesis of Saturated Heterocycles via Palladium-Catalyzed Alkene Carboetherification and Carboamination Reactions

M. Mkosza* M. Paszewski D. Sulikowski

Z Ph2PK+ NO2 liq NH3 KMnO4

NO2 O PPh2 + Z Z

NO2

PPh2

3370%

Letters

2938

Synthesis of Diphenyl(nitroaryl)phosphine Oxides via Oxidative Nucleophilic Substitution of Hydrogen in Nitroarenes with Diphenylphosphine Anion

Accounts

Asymmetric BaylisHillman Reaction: An Enchanting Expedition

VI

Table of Contents

Letters

2941

M. Adib* E. Sheibani L.-G. Zhu H. R. Bijanzadeh

Efficient Synthesis of Imidazo[2,1-b][1,3]benzothiazoles and 9H-Imidazo[1,2-a][1,3]benzimidazoles under Solvent-Free Conditions

R O X NH2 N + ArCHO + HN O ArHC N X = S, NH NH O solvent-free 200 C, 5 min R X N N Ar

2945

D. Shanmugapriya R. Shankar G. Satyanarayana V. H. Dahanukar U. K. S. Kumar* N. Vembu

Aerial Oxidation of 2,2-Dibromo-1-Aryl and Heteroaryl Ethanones: A Facile Synthesis of Aryl and Heteroaryl a-Keto Amides
O R1 Br Br HN R2 R2 O THF, air or O2 4050 C, 1824 h R1 R2 N R3

O 4861%

R1 = Ph, 3-Br-4-OMeC6H3, 4-NO2C6H4, 1-naphtyl, 1-thienyl, 2-BrC6H4 R2 HN R3 = morpholine, piperidine, pyrrolidine, N,N-dimethyl amine, N,Ndiethyl amine, N-methyl benzyl amine, 2-pipecolylmethyl ester

2951

E. Glvez R. Parell P. Romea* F. Urp*

Stereoselective Addition of Titanium Enolates to Functionalized Acetals: A Novel Approach to the g-Amino Acid of Bistramides and FR252921
S S N O 1) TiCl4, i-Pr2NEt 2) SnCl4, OR RO FG S N S O OR FG MeO O OBn FG

i-Pr

i-Pr

R = Me, Bn

FG = N3, NPhth -amino acid of bistramides and FR252921

2955

A. Seggio A. Jutand G. Priem F. Mongin*

Synthesis of Unsymmetrical Heterobiaryls Using Palladium-Catalyzed Cross-Coupling Reactions of Lithium Organozincates

1) BuLi or LTMP 2) ZnCl2TMEDA (0.33 equiv) 3) Cl X (X = CH, N) N ArH R PdCl2 (2 mol%), dppf (2 mol%) 55 C, 12 h 4) hydrolysis N R

Ar

Table of Contents

VII

A. Lindner A. Schmidt*

O N H S N Me RNH2

O N N Me
+

N H

H NH R

2965

F. Pfrengle V. Dekaris L. Schefzig R. Zimmer H.-U. Reissig*

Indium Trichloride Mediated Cleavage of Acetonides in the Presence of Acid-Labile Functional Groups Enhancing the Synthetic Utility of 1,3-Dioxolanyl-Substituted 1,2-Oxazines
O O N InCl3 (2 equiv), H2O (4 equiv) MeCN r.t. 5897% OH OH N

Bn

Bn

R = acid-labile groups

2969

T. Horneff T. Bach*

Synthesis of the C9C21 Fragment of Geldanamycin via a Diastereoselective Substrate-Controlled Hydrogenation

Oi-Pr MeO O diastereoselective hydrogenation
14

13 steps 22% overall OTIPS

NHZ Oi-Pr OTBDMS

MeO

Z = CO2Bn

MeO

2973

P. G. J. Plaza B. A. Bhongade G. Singh*

Synthesis of Chiral Carbohydrate Ionic Liquids

N O BnO BnO O O P O OBn O MeNImHCl BnO TMSOTf BnO OBn O
+

N X

X = Cl X = PF6 X = BF4

Letters

2961

N-Heterocyclic Carbenes of Indazole as Reagents: Indazol-3-ylideneMediated Syntheses of Amidines from Thiolactams of Pyrrolobenzodiazepines

VIII

Table of Contents

Letters

2977

D. Kawai K. Kawasumi T. Miyahara T. Hirashita* S. Araki

Cyclopropanation Mediated by Lithium Iodide of Electron-Deficient Alkenes with Activated Dibromomethylene Compounds
NC EWG Br EWG + Br Ph CN EWG Lil DMF, r.t. Ph EWG EWG EWG

2981

Y. Shimada H. Sato S. Mochizuki K. Matsumoto*

Preparation of Optically Active 1-O-Alkyl-3-O-arylsulfonyl-sn-glycerol Derivatives: Substrate Engineering in Enzyme-Mediated Enantioselective Hydrolysis
Ar = 3,5-Me2C6H3 R = PMB

O Ar S O O O Ar S O O

OAc OR

lipase PS bufferi-Pr2O 30 C O OR + Ar S O O OH

E value >200

OAc

OR

2985

I. S. Kim Q. R. Li G. R. Dong S. H. Woo H.-j. Park O. P. Zee Y. H. Jung*

A Concise Synthesis of (+)-Polyoxamic Acid and (+)-5-O-Carbamoyl Polyoxamic Acid

OBn RO OBn OBn R = Bn, H CSI Ph RO OBn NHCbz R = Bn 74%; syn/anti = 8.8:1 R = CONH2 63%; syn/anti = 7.2:1 Ph OBn RO OH NH2 OH O OH

(+)-polyoxamic acid (R = H) (+)-5-O-carbamoyl polyoxamic acidd (R = CONH2)

2989

X. Dai C. Cheng C. Ding Q. Yao A. Zhang*

Synthesis of 2,7-Naphthyridine-Containing Analogues of Luotonin A

O N EtO2C N Ar O N EtO2C O N H N O N N N O O N N H N O O O N O O N R N N N

Table of Contents

IX

B. Zhao J. Chang* Q. Wang Y. Du K. Zhao

N RO F O OAc persilylated 6-chloropurine DCE, SnCl4 0 C to r.t. RO F N O

N N N Cl K2CO3 MeOH reflux HO F N O OMe O 55% 01 N N

OBz R = 4-ClBz 7

OBz R = 4-ClBz 65% 9

2997

W. Du Y.-K. Liu L. Yue Y.-C. Chen*

Organocatalytic Asymmetric 1,3-Dipolar Cycloaddition of Nitrones to Nitroolefins

Ar1 R2 NO2 j1 R1 + (10 mol%) R1 N O O2N R2 Ar2 N HN Ar2 j1 HN Ar3 S

O Ar1 N MTBE, 4 MS 0 C, 6 d

up to 93% yield generally >99:1 dr, up to 88% ee

Ar2 = 3,5-F2C6H3 Ar3 = 3,5-(CF3)2C6H3

3001

R. Sarma D. Prajapati*

Ionic Liquid an Efficient Recyclable System for the Synthesis of 2,4-Disubstituted Quinolines via MeyerSchuster Rearrangement
Ar Ar O R NH2 [hmim]PF6 + Ph MS rearrangement O NH2 Ph H2O R N Ph Ar

3006

R. Sanz* V. Guilarte M. P. Castroviejo

Simple Indole Synthesis by One-Pot Sonogashira CouplingNaOH-Mediated Cyclization

R2 + I NH R1 R1 = H, Ac, Alk G = Hal, NO2, CN PdCl2(PPh3)2 (cat.) CuI (cat.), Et2NH DMF or DMA, r.t. NaOH (410 equiv) 140 C, 29 h, or MW (180 C), 1050 min G N R1 6089% R2

Letters

2993

Design and Synthesis of 3-Deoxy-3-Fluoro-2-O,3-C-Vinylene-Linked Bicyclic Purine Nucleoside

Table of Contents

Letters

3011

D. Ghosh L. Thander S. K. Ghosh S. K. Chattopadhyay*

Sequential Aza-Claisen Rearrangement and Ring-Closing Metathesis as a Route to 1-Benzazepine Derivatives

R2 N R1 R1 O N

3016

F. Olimpieri A. Volonterio* M. Zanda*

Three-Component, One-Pot Sequential Synthesis of 1,3-Disubstituted 5-Arylhydantoins

R1N3 O X Ar R3 + COOH + R2NCO R1, R2 = Alk, Ar R3 = H, Alk, Ar X = Br, Cl R1 N Ar R3 O N R2

3021

B. K. Singh V. S. Parmar E. Van der Eycken*

Rapid Palladium-Catalyzed C3-Arylation of 2(1H)-Pyrazinones: Effect of Simultaneous Cooling on Microwave-Assisted Reactions on Solid Support
PMB H CuTC, Pd(PPh3)4, THF B(OH)2 O + R CuTC, Pd(PPh3)4, THF MW and simultaneous liquid cooling H PMB N N O R Cl conventional conditions or MW and simultaneous air cooling H N O + Cl Cl N Ph N Ph H N O

PMB H N

Cl

3026

W. Prukaa*

A Novel Approach to Stilbenoid Dendrimer Core Synthesis

Me Si X Me
2

O Pd2(dba)3 dioxane 1,3,5-Br3C6H3 or 1,2,4,5-I4C6H2 R1 R3

R2 R1 R3

R1 = H, R2, R3 = or R1, R3 = R2 = H

Me 2X X = H, Br, Cl + Me

Me Me

[Ru] dioxane

Si O Si

7796%

Table of Contents

XI

G. Guillena* C. Njera* S. F. Vizquez

O R CHO R2
1

O R3 BzOH, cat. solvent-free R

3

OH R R2
1

OH R1

O R2 NH

iso anti R2, R3 = cycloalkyl; R2 = H, Me, OMe, SMe, R3 = Me or R2 = Me, R3 = H

dr up to 89:11, anti/syn up to 99:1; 7898% ee O O O
n

NH NHTs

O BzOH, cat. solvent-free O

n

8495%, 8390%

3036

W. Choung B. A. Lorsbach T. C. Sparks J. M. Ruiz M. J. Kurth*

4-(Isoxazol-3-yl)pyrimidines from Pyrimidinyl Nitrile Oxides

N R1 O OEt OEt R1 N N SMe OH R1 N HN N R3 N O R2

R2 = R, CONHR

3041

Y. Nishihara* E. Inoue Y. Okada K. Takagi

Sila-Sonogashira Cross-Coupling Reactions of Activated Aryl Chlorides with Alkynylsilanes

Ar1 + Ar2Cl TMS Pd(OAc)2 (cat.), ()-DIOP CuCl (cat.), DMF 120 C, 348 h non-basic conditions

Ar1

Ar2

17 examples

3046

W.-h. Ji Y.-m. Pan S.-y. Zhao Z.-p. Zhan*

FeCl3-Catalyzed PropargylationCycloisomerization Tandem Reaction: A Facile One-Pot Synthesis of Substituted Furans

O X R1 R2 X = OH, OAc + R3 O O R4 FeCl3 (5 mol%) toluene reflux, 0.54.5 h R
4

R1

R3

R2

Letters

3031

N-Tosyl-(Sa)-binam-L-prolinamide as Highly Efficient Bifunctional Organocatalyst for the General Enantioselective Solvent-Free Aldol Reaction

XII

Table of Contents

Letters

3053

Z. Li G. Deng Y.-C. Li*

Zinc(II) IodideTriethylsilane: A Novel Mild Reduction System for Direct Deoxygenation of Aryl Aldehydes, Ketones, and a,b-Unsaturated Enones
O R1 R2 ZnI2 (2 equiv) TESH (10 equiv) DCE r.t. to 60 C, 548 h H H R1 R2

R1 = aryl, alkyl, alkenyl R2 = H, aryl, alkyl, alkenyl ...

2598%

3058

L. Shen J. Zhang S. Cao* J. Yu N. Liu J. Wu X. Qian*

One-Pot Synthesis of Trifluoromethyl-Containing Pyrazoles via Sequential Yb(PFO)3-Catalyzed Three-Component Reaction and IBX-Mediated Oxidation
O F3C + R1CHO 1 R2NHNH2 2 O R2 OEt Yb(PFO)3 (5 mol%) neat, 120 C R1 CO2Et 4 N N CF3 R1 CO2Et n a5 IBX N R2 N CF3

3063

H.-J. Xu X.-Y. Zhao Y. Fu* Y.-S. Feng*

Ligand-Free CS Bond Formation Catalyzed by Copper(I) Oxide

R1I + R2SH Cu2O (5 mol%) KOH (2 equiv), DMSOH2O (4:1) Ar, 80 C, 24 h R1 S R2

R1 = Ar, heteroaryl R2 = Ar, Alk, heteroaryl

6096%

3068

J.-P. Wan Y.-F. Chai J.-M. Wu Y.-J. Pan*

N,N-(Phenylmethylene)diacetamide Analogues as Economical and Efficient Ligands in Copper-Catalyzed Arylation of Aromatic Nitrogen-Containing Heterocycles
Z X Z + HetNH NaOMe, DMSO 90130 C, 12 h L CuI (10%), (10%) Z NHet Z

Z = CH, N; X = Cl, Br, I; HetNH = [2-methyl]imidazole, [2-methyl]benzimidazole, pyrrole, indole, benzotriazole R2 = O N H N H O

1 2

R1

R2

O R1CHO + R2 NH2

R = aryl, alkyl; R = alkyl, amino

Table of Contents

XIII

Compiled by S. Yaragorla

3075

Compiled by F. L. S. da Machado

Nitrosobenzene

XVII

Forthcoming Articles

Spotlights

3073

Lithium Aluminum Hydride: A Powerful Reducing Agent

XIV

Table of Contents

Author Index
Adib, M. 2941 Araki, S. 2977 Bach, T. 2969 Bhongade, B. A. 2973 Bijanzadeh, H. R. 2941 Cao, S. 3058 Castroviejo, M. P. 3006 Chai, Y.-F. 3068 Chang, J. 2993 Chattopadhyay, S. K. 3011 Chen, Y.-C. 2997 Cheng, C. 2989 Choung, W. 3036 Dahanukar, V. H. 2989 Dai, X. 2989 da Machado, F. L. S. 3075 Dekaris, V. 2965 Deng, G. 3053 Ding, C. 2989 Dong, G. R. 2985 Du, W. 2997 Du, Y. 2993 Feng, Y.-S. 3063 Fu, Y. 3063 Glvez, E. 2951 Ghosh, D. 3011 Ghosh, S. K. 3011 Guilarte, V. 3006 Guillena, G. 3031 Hirashita, T. 2977 Horneff, T. 2969 Inoue, E. 3041 Ji, W.-h. 3046 Jung, Y. H. 2985 Jutand, A. 2955 Kawai, D. 2977 Kawasumi, K. 2977 Kim, I. S. 2985 Krishna, P. R. 2897 Kumar, U. K. S. 2945 Kurth, M. J. 3036 Li, Q. R. 2985 Li, Y.-C. 3053 Li, Z. 3053 Lindner, A. 2961 Liu, N. 3058 Liu, Y.-K. 2997 Lorsbach, B. A. 3036 Mkosza, M. 2938 Matsumoto, K. 2981 Miyahara, T. 2977 Mochizuki, S. 2981 Mongin, F. 2955 Njera, C. 3031 Nishihara, Y. 3041 Okada, Y. 3041 Olimpieri, F. 3016 Pan, Y.-J. 3068 Pan, Y.-m. 3046 Parell, R. 2951 Park, H.-j. 2985 Parmar, V. S. 3021 Paszewski, M. 2938 Pfrengle, F. 2965 Plaza, P. G. J. 2973 Prajapati, D. 3001 Priem, G. 2955 Prukaa, W. 3026 Qian, X. 3058 Reddy, P. S. 2897 Reissig, H.-U. 2965 Romea, P. 2951 Ruiz, J. M. 3036 Sachwani, R. 2897 Sanz, R. 3006 Sarma, R. 3001 Sato, H. 2981 Satyanarayana, G. 2945 Schefzig, L. 2965 Schmidt, A. 2961 Seggio, A. 2955 Shankar, R. 2945 Shanmugapriya, D. 2945 Sheibani, E. 2941 Shen, L. 3058 Shimada, Y. 2981 Singh, B. K. 3021 Singh, G. 2973 Sparks, T. C. 3036 Sulikowski, D. 2938 Takagi, K. 3041 Thander, L. 3011 Urp, F. 2951 Van der Eycken, E. 3021 Vembu, N. 2945 Vizquez, S. F. 3031 Volonterio, A. 3016 Wan, J.-P. 3068 Wang, Q. 2993 Wolfe, J. P. 2913 Woo, S. H. 2985 Wu, J. 3058 Wu, J.-M. 3068 Xu, H.-J. 3063 Yao, Q. 2989 Yaragorla, S. 3073 Yu, J. 3058 Yue, L. 2997 Zanda, M. 3016 Zee, O. P. 2985 Zhan, Z.-p. 3046 Zhang, A. 2989 Zhang, J. 3058 Zhao, B. 2993 Zhao, K. 2993 Zhao, S.-y. 3046 Zhao, X.-Y. 3063 Zhu, L.-G. 2941 Zimmer, R. 2965