1.3 Metal-Catalyzed Intramolecular Allylic Substitution Reactions

This review highlights recent developments in the area of transition metal-catalyzed allylic substitution reactions with unactivated allylic substrates.

ChemInform Abstract: Transition-Metal-Catalyzed Allylic Substitution Reactions: Stereoselective Construction of α- and β-Substituted Carbonyl Compounds

ChemInform ◽

10.1002/chin.201410252 ◽

2014 ◽

Vol 45 (10) ◽

pp. no-no

Author(s):

Samuel Oliver ◽

P. Andrew Evans

Keyword(s):

Transition Metal ◽

Carbonyl Compounds ◽

Allylic Substitution ◽

Substitution Reactions ◽

Iridium-catalyzed Z-retentive asymmetric allylic substitution reactions

Science ◽

10.1126/science.abd6095 ◽

2021 ◽

Vol 371 (6527) ◽

pp. 380-386 ◽

Cited By ~ 1

Author(s):

Ru Jiang ◽

Lu Ding ◽

Chao Zheng ◽

Shu-Li You

Keyword(s):

Transition Metal ◽

Optically Active ◽

Promising Method ◽

Allylic Substitution ◽

Substitution Reactions ◽

Metal Catalyzed ◽

Quaternary Stereocenter ◽

Thermodynamic Instability

Z-Olefins are challenging synthetic targets owing to their relative thermodynamic instability. Transition metal–catalyzed asymmetric allylic substitution reactions are well known for installing stereocenters adjacent to branched or E-linear olefins. However, analogous reactions for the synthesis of optically active Z-olefin products are rare. Here we report iridium-catalyzed asymmetric allylic substitution reactions that retain Z-olefin geometries while establishing an adjacent quaternary stereocenter. The formation of transient anti-π-allyl-iridium intermediates and their capture by external nucleophiles before isomerization to the thermodynamically more stable syn-π-allyl-iridium counterparts have been observed. These results provide a promising method for preparing chiral Z-olefinic compounds.

ChemInform Abstract: Transition Metal-Catalyzed Allylic Substitution Reactions with Unactivated Allylic Substrates

ChemInform ◽

10.1002/chin.201551215 ◽

2015 ◽

Vol 46 (51) ◽

pp. no-no

Author(s):

Nicholas A. Butt ◽

Wanbin Zhang

Keyword(s):

Transition Metal ◽

Allylic Substitution ◽

Substitution Reactions ◽

Transition-Metal-Catalyzed Allylic Substitution Reactions: Stereoselective Construction of α- and β-Substituted Carbonyl Compounds

Synthesis ◽

10.1055/s-0033-1338538 ◽

2013 ◽

Vol 45 (23) ◽

pp. 3179-3198 ◽

Cited By ~ 71

Author(s):

P. Evans ◽

Samuel Oliver

Keyword(s):

Transition Metal ◽

Carbonyl Compounds ◽

Allylic Substitution ◽

Substitution Reactions ◽

Silicon Grignard Reagents as Nucleophiles in Transition-Metal-Catalyzed Allylic Substitution

Synthesis ◽

10.1055/s-0037-1610309 ◽

2018 ◽

Vol 51 (01) ◽

pp. 233-239 ◽

Cited By ~ 9

Author(s):

Weichao Xue ◽

Martin Oestreich

Keyword(s):

Transition Metal ◽

Metal Catalysts ◽

Transition Metal Catalysts ◽

Grignard Reagents ◽

Allylic Substitution ◽

Substitution Reactions ◽

Cyclic System ◽

Leaving Group ◽

A broad range of transition-metal catalysts is shown to promote allylic substitution reactions of allylic electrophiles with silicon Grignard reagents. The procedure was further elaborated for CuI as catalyst. The regioselectively is independent of the leaving group for primary allylic precursors, favoring α over γ. The stereochemical course of this allylic transposition was probed with a cyclic system, and anti-diastereoselectivity was obtained.