Asymmetric Rhodium-Catalyzed Allylic Substitution Reactions with Nitrile-Stabilized Carbanions

Synlett ◽  
2021 ◽  
Author(s):  
Mai-Jan Tom ◽  
P. Andrew Evans
Keyword(s):  
Biologically Active ◽  
Allylic Alkylation ◽  
Substitution Reactions ◽  
Stereogenic Centers ◽  
Enantioselective Reactions ◽  
Catalyzed Reactions ◽  
Metal Catalyzed ◽  
Alkylation Reactions ◽  
Quaternary Stereogenic Centers ◽  
Selective Access

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 recently developed both enantiospecific and enantioselective allylic alkylation reactions. Notably, these novel reactions permit the expedient and selective access to an array of acyclic ternary and quaternary stereogenic centers that are present in important biologically active molecules. 1 Introduction 2 Enantiospecific Reactions of Nitrile-Stabilized Anions 3 Enantioselective Reactions of Nitrile-Stabilized Anions 4 Conclusion

scholarly journals Enantioselective synthesis of gem-diarylalkanes by transition metal-catalyzed asymmetric arylations (TMCAAr)

2018 ◽  
Vol 9 (3) ◽  
pp. 546-559 ◽  
Author(s):  
Tao Jia ◽  
Peng Cao ◽  
Jian Liao
Keyword(s):  
Transition Metal ◽  
Enantioselective Synthesis ◽  
Transfer Reactions ◽  
Stereogenic Centers ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed ◽  
Quaternary Stereogenic Centers ◽  
Aryl Transfer

To date, enantiomerically enriched molecules containing gem(1,1)-diaryl containing tertiary or quaternary stereogenic centers have been readily accessed by transition metal-catalyzed enantioselective or stereoconvergent aryl transfer reactions.

Transition metal-catalyzed reactions in heterocyclic chemistry

2002 ◽  
Vol 74 (8) ◽  
pp. 1327-1337 ◽  
Author(s):  
Irina P. Beletskaya
Keyword(s):  
Transition Metal ◽  
Heterocyclic Compounds ◽  
Heterocyclic Chemistry ◽  
Substitution Reactions ◽  
Multiple Bonds ◽  
Palladium Catalyzed ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed

The palladium-catalyzed substitution reactions forming carbon­carbon and carbon­element bonds, as well as nickel-catalyzed addition of E­H and E­E' bonds across multiple bonds, are considered in their application to the chemistry of heterocyclic compounds.

scholarly journals Recent Advances in Transition Metal-Catalyzed Reactions of Oxabenzonorbornadiene

2019 ◽  
Vol 16 (4) ◽  
pp. 460-484 ◽  
Author(s):  
Rebecca Boutin ◽  
Samuel Koh ◽  
William Tam
Keyword(s):  
Transition Metal ◽  
Structural Features ◽  
Metal Catalysts ◽  
Single Step ◽  
Transition Metal Catalysts ◽  
Biologically Active ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed ◽  
Work Done

Background: Oxabenzonorbornadiene (OBD) is a useful synthetic intermediate capable of undergoing multiple types of transformations due to three key structural features: a free alkene, a bridged oxygen atom, and a highly strained ring system. Most notably, ring-opening reactions of OBD using transition metal catalysts and nucleophiles produce multiple stereocenters in a single step. The resulting dihydronaphthalene framework is found in many natural products, which have been shown to be biologically active. Objective: This review will provide an overview of transition metal-catalyzed reactions from the past couple of years including cobalt, copper, iridium, nickel, palladium and rhodium- catalyzed reactions. In addition, the recent derivatization of OBD to cyclopropanated oxabenzonorbornadiene and its reactivity will be discussed. Conclusion: It can be seen from the review, that the work done on this topic has employed the use of many different transition metal catalysts, with many different nucleophiles, to perform various transformations on the OBD molecule. Additionally, depending on the catalyst and ligand used, the stereo and regioselectivity of the product can be controlled, with proposed mechanisms to support the understanding of such reactions. The use of palladium has also generated a cyclopropanated OBD, with reactivity similar to that of OBD. An additional reactive site exists at the distal cyclopropane carbon, giving rise to three types of ring-opened products.

Enantioselective Synthesis of Tertiary and Quaternary Stereogenic Centers: Copper/Phosphoramidite-Catalyzed Allylic Alkylation with Organolithium Reagents

2012 ◽  
Vol 124 (8) ◽  
pp. 1958-1961 ◽  
Author(s):  
Martín Fañanás-Mastral ◽  
Manuel Pérez ◽  
Pieter H. Bos ◽  
Alena Rudolph ◽  
Syuzanna R. Harutyunyan ◽  
...  
Keyword(s):  
Enantioselective Synthesis ◽  
Allylic Alkylation ◽  
Stereogenic Centers ◽  
Organolithium Reagents ◽  
Quaternary Stereogenic Centers
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