Allylic Alcohols: Sustainable Sources for Catalytic Enantioselective Alkylation Reactions

2011 ◽  
Vol 50 (5) ◽  
pp. 994-995 ◽  
Author(s):  
Marco Bandini
Keyword(s):  
Allylic Alcohols ◽  
Enantioselective Alkylation ◽  
Alkylation Reactions

scholarly journals Iridium-Catalyzed Asymmetric α-Allylic Alkylation of Amides using Vinyl Azide as Amide Enolate Surrogate

2020 ◽  
Author(s):  
Aditya Chakrabarty ◽  
Santanu Mukherjee
Keyword(s):  
Electronic Properties ◽  
Reaction Pathways ◽  
Allylic Alcohols ◽  
Allylic Alkylation ◽  
Atom Economy ◽  
Asymmetric Allylic Alkylation ◽  
Vinyl Azides ◽  
Alkylation Reactions ◽  
First Time

Among the unstabilized enolates used as nucleophile in iridium-catalyzed asymmetric allylic alkylation reactions, amide enolates are least explored. Vinyl azides are now employed as amide enolate surrogate for the first time in Ir-catalyzed asymmetric allylic alkylation with branched allylic alcohols as the allylic electrophile. Competing reaction pathways are suppressed through systematic tuning of steric and electronic properties of vinyl azide to effect α-allylic alkylation of secondary acetamides with high atom-economy, exclusive branched selectivity and moderate to excellent enantioselectivity.<br>

Allylic alcohols: Valuable synthetic equivalents of non-activated alkenes in gold-catalyzed enantioselective alkylation of indoles

2011 ◽  
Vol 696 (1) ◽  
pp. 338-347 ◽  
Author(s):  
Marco Bandini ◽  
Andrea Gualandi ◽  
Magda Monari ◽  
Alessandro Romaniello ◽  
Diego Savoia ◽  
...  
Keyword(s):  
Allylic Alcohols ◽  
Enantioselective Alkylation

scholarly journals Iridium-Catalyzed Asymmetric α-Allylic Alkylation of Amides using Vinyl Azide as Amide Enolate Surrogate

2020 ◽  
Author(s):  
Aditya Chakrabarty ◽  
Santanu Mukherjee
Keyword(s):  
Electronic Properties ◽  
Reaction Pathways ◽  
Allylic Alcohols ◽  
Allylic Alkylation ◽  
Atom Economy ◽  
Asymmetric Allylic Alkylation ◽  
Vinyl Azides ◽  
Alkylation Reactions ◽  
First Time

Among the unstabilized enolates used as nucleophile in iridium-catalyzed asymmetric allylic alkylation reactions, amide enolates are least explored. Vinyl azides are now employed as amide enolate surrogate for the first time in Ir-catalyzed asymmetric allylic alkylation with branched allylic alcohols as the allylic electrophile. Competing reaction pathways are suppressed through systematic tuning of steric and electronic properties of vinyl azide to effect α-allylic alkylation of secondary acetamides with high atom-economy, exclusive branched selectivity and moderate to excellent enantioselectivity.<br>

scholarly journals CuH-Catalyzed Enantioselective Alkylation of Indole Derivatives with Ligand-Controlled Regiodivergence

2018 ◽  
Author(s):  
Yuxuan Ye ◽  
Seoung-Tae Kim ◽  
Jinhoon Jeong ◽  
Mu-Hyun Baik ◽  
Stephen L. Buchwald
Keyword(s):  
Organic Chemistry ◽  
Organic Synthesis ◽  
Density Functional ◽  
Copper Hydride ◽  
Indole Derivatives ◽  
Functional Theory ◽  
Ligand Density ◽  
Significant Challenge ◽  
Enantioselective Alkylation ◽  
Alkylation Reactions

<b>Enantioenriched molecules bearing indole-substituted stereocenters form a class of privileged compounds in biological, medicinal, and organic chemistry. Thus, the development of methods for asymmetric indole alkylation is highly valuable in organic synthesis. Traditionally, achieving N-selectivity in indole alkylation reactions is a significant challenge, since there is an intrinsic preference for alkylation at C3, the most nucleophilic position. Furthermore, selective and predictable access to either N- and C3-alkylated chiral indoles using catalyst control has been a long-standing goal in indole functionalization. Herein, we report a ligand-controlled regiodivergent synthesis of N- and C3-alkylated chiral indoles that relies on a polarity reversal strategy. In contrast to conventional alkylation reactions in which indoles are employed as nucleophiles, this transformation employs electrophilic indole derivatives, N-(benzoyloxy)indoles, as coupling partners. N- or C3-alkylated indoles are prepared with high levels of regio- and enantioselectivity using a copper hydride catalyst. The regioselectivity is governed by the use of either DTBM-SEGPHOS or Ph-BPE as the supporting ligand. Density functional theory (DFT) calculations are conducted to elucidate the origin of the ligand-controlled regiodivergence.</b>

Sign in / Sign up

Export Citation Format

Share Document