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Title: Metal Carbene-Directed Intramolecular Vinylogous Reactions of Vinyldiazoacetates
Intramolecular addition reactions of electrophilic metallovinylcarbenes with nucleophiles that do not have access to the carbene center undergo addition to the vinylogous position, forming products that rely on subsequent transformations of vinylmetal intermediates. Catalytic addition to a carbon-carbon double bond elicits the formation of an intermediate carbocation whose proton loss causes protodemetalation of the vinylmetal intermediate. Addition to the azido group results in the formation of aliphatic 1,2,3-triazines by [3 + 3]-cycloaddition. Catalytic intramolecular reactions with a carbamate nucleophile yield a carbonyl ylide whose loss of isobutylene produces oximidovinyl-oxazolidinone esters with high enantioselectivity. Comparisons are made between rhodium, copper, gold, and silver catalysts  more » « less
Award ID(s):
2054845
PAR ID:
10554890
Author(s) / Creator(s):
; ; ; ;
Editor(s):
Crudden, Cathleen
Publisher / Repository:
American Chemical Society
Date Published:
Journal Name:
ACS Catalysis
Volume:
14
ISSN:
2155-5435
Page Range / eLocation ID:
16618 to 16623
Subject(s) / Keyword(s):
intramolecular reactions, vinyldiazo compounds, metallovinylcarbenes, electrophilic addition, catalysis
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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