Enantiodivergent Synthesis of Tertiary α-Aryl 1-Indanones: Evidence Toward Disparate Mechanisms in the Palladium-Catalyzed Decarboxylative Asymmetric Protonation.

Content Provider	Semantic Scholar
Author	Kingston, Cian Guiry, Patrick J.
Copyright Year	2017
Abstract	Herein, we describe a study into the scope and origin of an enantiodivergent effect in the palladium-catalyzed decarboxylative asymmetric protonation. By switching the achiral proton source, both enantiomers of a series of tertiary α-aryl-1-indanones are readily accessed from the corresponding α-aryl-β-keto allyl esters. In this example of dual stereocontrol, enantioselectivities up to 94% (S) and 92% (R) were achieved using Meldrum's acid and formic acid, respectively. In an attempt to rationalize this switch in absolute configuration an investigation of the ambiguous mechanism of the decarboxylative asymmetric protonation was conducted. A novel catalytic cycle for the reaction with formic acid is proposed and subjected to a variety of experimental studies.
Starting Page	3806
Ending Page	3819
Page Count	14
File Format	PDF HTM / HTML
Alternate Webpage(s)	http://www.sspc.ie/sites/default/files/Cian%20JOC%20Published%202017.pdf
PubMed reference number	28345917v1
Alternate Webpage(s)	https://doi.org/10.1021/acs.joc.7b00303
DOI	10.1021/acs.joc.7b00303
Journal	The Journal of organic chemistry
Volume Number	82
Issue Number	7
Language	English
Access Restriction	Open
Subject Keyword	Carnitine esters/Creatinine:MRto:Pt:Urine:Qn Dual Esters Palladium Protons Tertiary Care Centers Thioctic Acid formic acid
Content Type	Text
Resource Type	Article