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

(selective for aldehydes in presence of other carbonyls)

(aldehydes, ketones, imines; not esters, amides)
(electrophilic)
(nucleophilic)
(Superhydride; very nucleophilic)

Examples:
Reduction of Ketone in Presence of Aldehyde
1. LiHMDS

Me
Me

Me
Me

2. DIBAL

Me

Me
HO

MeO2C
O

O
via:

Me
Me

Me

MeO2C
LiO

Lecture 8 Wednesday 19.10.2011

Enone Reduction

Olefins
Hydrogenation most common!
Catalysts

Pd
Pt
Ir

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

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
classical version

1. NaH
2. CS2
3. MeI
R OH

S
R

R H
O

SMe

xanthate
BEt3, O2, H2O
more modern

Lecture 8 Wednesday 19.10.2011

Myers-Movassaghi

Thiols / Thioethers
Raney Nickel frequently used!

Oxidation
Alcohols

TEMPO

(selective for primary alcohols)

Classical Version: TEMPO, NaOCl, biphasic

Activated DMSO Oxidations

Swern:

DMSO, (COCl)2, NEt3

Parikh-Doering:

DMSO, SO3py, NEt3

Corey-Kim:

DMS, NCS, NEt3

Ley Oxidation:

TPAP (or TBAP), NMO, 4 molecular sieves, DCM

Chromates:

PDC, PCC, Jones reagent

Lecture 8 Wednesday 19.10.2011

Hypervalent Iodides:

DMP, IBX, Ph-I(OAc)2

Manganese Dioxide

(for allylic alcohols)

Pinnick

(aldehyde to acid, NaClO2, NaH2PO4, 2-methylbut-2-ene)

Olefins

To Epoxide:

mCPBA, DMDO, VO(acac)2, H2O2 / KOH

To Diol:

OsO4 (cat.), NMO

Allylic Oxidation:

SeO2

Oxidative Cleavage:

O3 / PPh3, OsO4 / NaIO4

Ketones to Enones

Saegusa

Selenoxide Elimination

DDQ

Mukaiyama Oxidation

Lecture 8 Wednesday 19.10.2011

Common Bases

Strong:

LDA, LiHMDS, KHMDS, NaHMDS, t-BuLi, sec-BuLi, n-BuLi

Intermediate:

DBU, t-BuOK

Weak:

NEt3, DIPEA, pyridine

Common Acids

Strong:

triflic acid, HCl

Intermediate:

trifluoroacetic acid, acetic acid

Weak:

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