OC VIII - Fall 2011

Commonly Used Reagents in Organic Synthesis

This summary gives a short overview of common reagents and reaction protocols used in organic synthesis with focus on reduction and oxidation reactions. Furthermore, some recent methods that can be employed to effect standard transformations are featured. The list is by no means complete nor does it cover the full scope and limitations of the single methods. In order to gain a profound understanding of organic reactivity the reader is highly encouraged to consult advanced organic chemistry textbooks and the original literature.

Reduction
Carbonyls NaBH(OAc)3 NaBH4 DIBAL LiAlH4 LiBEt3H Examples: Reduction of Ketone in Presence of Aldehyde
Me Me MeO2C O via: Me MeO2C LiO Me Me Me 1. LiHMDS 2. DIBAL Me HO O Me Me

(selective for aldehydes in presence of other carbonyls) (aldehydes, ketones, imines; not esters, amides) (electrophilic) (nucleophilic) (Superhydride; very nucleophilic)

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Enone Reduction

Olefins Hydrogenation most common! Catalysts Pd Pt Ir Alkynes To Z-Alkene: Lindlar hydrogenation: H2, Pd, Pb + quinoline To E-Alkene: Birch conditions: Li, NH3 Halogens Bu3SnH, AIBN (or other radical starter) Alcohols Barton-McCombie
Bu3SnH, AIBN 1. NaH 2. CS2 3. MeI R OH R O classical version S R H SMe xanthate BEt3, O2, H2O more modern

(most frequent) (for amines) (for fully substituted olefins; cf. Crabtrees catalyst)

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Myers-Movassaghi

Thiols / Thioethers Raney Nickel frequently used!

Oxidation
Alcohols TEMPO (selective for primary alcohols)

Classical Version: TEMPO, NaOCl, biphasic Activated DMSO Oxidations

Swern: Parikh-Doering: Corey-Kim: Ley Oxidation: Chromates:

DMSO, (COCl)2, NEt3 DMSO, SO3py, NEt3 DMS, NCS, NEt3 TPAP (or TBAP), NMO, 4 molecular sieves, DCM PDC, PCC, Jones reagent
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Hypervalent Iodides: Manganese Dioxide Pinnick Olefins To Epoxide: To Diol: Allylic Oxidation: Oxidative Cleavage:

DMP, IBX, Ph-I(OAc)2 (for allylic alcohols) (aldehyde to acid, NaClO2, NaH2PO4, 2-methylbut-2-ene)

mCPBA, DMDO, VO(acac)2, H2O2 / KOH OsO4 (cat.), NMO SeO2 O3 / PPh3, OsO4 / NaIO4

Ketones to Enones Saegusa

Selenoxide Elimination

DDQ

Mukaiyama Oxidation

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Common Bases Strong: Intermediate: Weak: LDA, LiHMDS, KHMDS, NaHMDS, t-BuLi, sec-BuLi, n-BuLi DBU, t-BuOK NEt3, DIPEA, pyridine

Common Acids Strong: Intermediate: Weak: triflic acid, HCl trifluoroacetic acid, acetic acid phenol, hexafluoroisopropanol

Reactivity of Organometallics RLi > RMgX > RAlR2 > RZnX

Common Sources of Palladium (as Catalyst Precursor) Pd(PPh3)4 Pd(dppf)Cl2 Pd(OAc)2 Pd2(dba)3

Lecture 8 Wednesday 19.10.2011