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Synlett 2022; 33(10): 939-951
DOI: 10.1055/a-1696-5713
DOI: 10.1055/a-1696-5713
account
Asymmetric Rhodium-Catalyzed Allylic Substitution Reactions with Nitrile-Stabilized Carbanions
We sincerely thank the National Sciences and Engineering Research Council (NSERC) for a Discovery Grant and Queen’s University for generous financial support. NSERC is also thanked for supporting a Tier 1 Canada Research Chair (P.A.E). We acknowledge the Huxiang High-Level Talent Gathering Project from the Science and Technology Department of Hunan Province (Grant No. 2020RC5001). We thank Queen’s University for R. S. McLaughlin Fellowships (M.-J.T.) and the Government of Ontario for a Queen Elizabeth II Graduate Scholarship in Science and Technology (M.-J.T.) and Ontario Graduate Scholarships (M.-J.T.).
Abstract
This Account summarizes our recent work on rhodium-catalyzed allylic alkylation reactions with nitrile-stabilized carbanions. Despite the challenges associated with employing nitrile-stabilized nucleophiles in transition-metal-catalyzed reactions, we have developed enantiospecific and enantioselective allylic alkylation reactions. Notably, these novel reactions permit expedient and selective access to an array of acyclic ternary and quaternary stereogenic centers present in important biologically active and functional molecules.
1 Introduction
2 Enantiospecific Allylic Alkylation Reactions with Nitrile-Stabilized Anions
3 Enantioselective Allylic Alkylation Reactions with Nitrile-Stabilized Anions
4 Conclusion
Key words
allylic alkylation - enantioselective - enantiospecific - nitrile anion - regioselective - total synthesisPublication History
Received: 19 August 2021
Accepted after revision: 15 November 2021
Accepted Manuscript online:
15 November 2021
Article published online:
24 May 2022
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For the pK a of nitriles, see:
For examples of nitriles coordinating to rhodium, see:
TM-catalyzed allylic alkylation of enolates and enolate equivalents:
For select examples, see:
For selected examples of (trimethylsilyl)acetonitrile undergoing 1,4-addition in the absence of copper, see:
For recent reviews, please see: