Enantiomerically Enriched Allylic Alcohols and Allylic Amines via C–C Bond-Forming Hydrogenation: Asymmetric Carbonyl and Imine Vinylation

Organic radicals are generally short-lived intermediates with exceptionally high reactivity. Strategically, achieving synthetically useful transformations mediated by organic radicals requires both efficient initiation and selective termination events. Here, we report a new catalytic strategy, namely bimetallic radical redox-relay, in the regio- and stereoselective rearrangement of epoxides to allylic alcohols. This approach exploits the rich redox chemistry of Ti and Co complexes and merges reductive epoxide ring opening (initiation) with hydrogen atom transfer (termination). Critically, upon effecting key bond-forming and -breaking events, Ti and Co catalysts undergo proton-transfer/electron-transfer with one another to achieve turnover, thus constituting a truly synergistic dual catalytic system.<br>

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ChemInform Abstract: Rh-Catalyzed C-C Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or Other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines.

ChemInform ◽

10.1002/chin.201319156 ◽

2013 ◽

Vol 44 (19) ◽

pp. no-no

Author(s):

Xi-Sha Zhang ◽

Yang Li ◽

Hu Li ◽

Kang Chen ◽

Zhi-Quan Lei ◽

...

Keyword(s):

Nucleophilic Addition ◽

Allylic Alcohols ◽

Allylic Amines

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Iridium-Catalyzed Synthesis of Primary Allylic Amines from Allylic Alcohols: Sulfamic Acid as Ammonia Equivalent

Angewandte Chemie International Edition ◽

10.1002/anie.200700159 ◽

2007 ◽

Vol 46 (17) ◽

pp. 3139-3143 ◽

Cited By ~ 293

Author(s):

Christian Defieber ◽

Martin A. Ariger ◽

Patricia Moriel ◽

Erick M. Carreira

Keyword(s):

Sulfamic Acid ◽

Allylic Alcohols ◽

Allylic Amines

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A Facile Highly Regio- and Stereoselective Preparation ofN-Tosyl Allylic Amines from Allylic Alcohols and Tosyl Isocyanate via Palladium(II)-Catalyzed Aminopalladation−β-Heteroatom Elimination

Organic Letters ◽

10.1021/ol006130u ◽

2000 ◽

Vol 2 (15) ◽

pp. 2357-2360 ◽

Cited By ~ 41

Author(s):

Aiwen Lei ◽

Xiyan Lu

Keyword(s):

Allylic Alcohols ◽

Allylic Amines

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Allylic Amines via Iridium-Catalyzed C-C Bond-Forming Hydrogenation

Synfacts ◽

10.1055/s-2007-968827 ◽

2007 ◽

Vol 2007 (09) ◽

pp. 0976-0976

Keyword(s):

Allylic Amines ◽

Bond Forming

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Highly enantioselective isomerization of primary allylic alcohols catalyzed by (P,N)-iridium complexes

Pure and Applied Chemistry ◽

10.1351/pac-con-09-09-10 ◽

2010 ◽

Vol 82 (7) ◽

pp. 1461-1469 ◽

Cited By ~ 15

Author(s):

Luca Mantilli ◽

David Gérard ◽

Sonya Torche ◽

Céline Besnard ◽

Clément Mazet

Keyword(s):

Asymmetric Catalysis ◽

Organic Synthesis ◽

Industrial Application ◽

Allylic Alcohols ◽

Iridium Complexes ◽

Allylic Amines ◽

Reaction Conditions ◽

Significant Challenge ◽

Catalytic Asymmetric

The catalytic asymmetric isomerization of allylic amines to enamines stands out as one of the most accomplished and well-studied reactions in asymmetric catalysis as illustrated by its industrial application. In contrast, the related asymmetric isomerization of primary allylic alcohols to the corresponding aldehydes still constitutes a significant challenge in organic synthesis. Herein, we show that under appropriate reaction conditions, iridium-hydride catalysts promote the isomerization of primary allylic alcohols under very mild reaction conditions. The best catalysts deliver the desired chiral aldehydes with unprecedented levels of enantioselectivity and good yields. Mechanistic hypotheses have been drawn based on preliminary investigations.

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Accessing chemical diversity by stereoselective gold-catalyzed manipulation of allylic and propargylic alcohols

Pure and Applied Chemistry ◽

10.1351/pac-con-11-09-05 ◽

2012 ◽

Vol 84 (8) ◽

pp. 1673-1684 ◽

Cited By ~ 20

Author(s):

Gianpiero Cera ◽

Michel Chiarucci ◽

Marco Bandini

Keyword(s):

Alkylating Agents ◽

Chemical Diversity ◽

Direct Access ◽

Allylic Alcohols ◽

Propargylic Alcohols ◽

Bond Forming ◽

Direct Activation ◽

Combined Use

The combined use of asymmetric Au(I) catalysis with allylic as well as propargylic alcohols proved to be a competent synthetic tool, toward the realization of complex molecular organic architectures in a stereochemically defined manner. In particular, allylic alcohols have been utilized as alkylating agents in the synthesis of tetrahydrocarbazoles/carbolines and morpholines by means of new C–C and C–X bond-forming processes. Analogously, the direct activation of indole-propargylic alcohols with cationic Au complexes opened a direct access to tetracyclic fused indolines in a highly stereoselective manner.

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