NDLI: The origin of the ligand-controlled regioselectivity in Rh-catalyzed [(2 + 2) + 2] carbocyclizations: steric <i>vs.</i> stereoelectronic effects

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The origin of the ligand-controlled regioselectivity in Rh-catalyzed [(2 + 2) + 2] carbocyclizations: steric vs. stereoelectronic effects

Content Provider	Royal Society of Chemistry (RSC)
Author	Crandell, Douglas W. Baik, Mu-Hyun Mazumder, Shivnath Evans, P. Andrew
Copyright Year	2015
Abstract	Density functional theory calculations demonstrate that the reversal of regiochemical outcome of the addition for substituted methyl propiolates in the rhodium-catalyzed [(2 + 2) + 2] carbocyclization with PPh3 and (S)-xyl-binap as ligands is both electronically and sterically controlled. For example, the ester functionality polarizes the alkyne π* orbital to favor overlap of the methyl-substituted terminus of the alkyne with the pπ-orbital of the alkenyl fragment of the rhodacycle during alkyne insertion with PPh3 as the ligand. In contrast, the sterically demanding xyl-binap ligand cannot accommodate the analogous alkyne orientation, thereby forcing insertion to occur at the sterically preferred ester terminus, overriding the electronically preferred orientation for alkyne insertion.
Starting Page	6896
Ending Page	6900
Page Count	5
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	6
Issue Number	12
Journal	Chemical Science
DOI	10.1039/c5sc02307f
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Subscribed
Subject Keyword	Ester Ligand Density functional theory Alkyne
Content Type	Text
Resource Type	Article
Subject	Chemistry

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