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

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Title
The origin of the ligand-controlled regioselectivity in Rh-catalyzed [(2 + 2) + 2] carbocyclizations: steric vs. stereoelectronic effects
Author(s)
Crandell, D.W.; Mazumder, S.; Evans, P.A.; Mu-Hyun Baik
Publication Date
2015-12
Journal
CHEMICAL SCIENCE, v.6, no.12, pp.6896 - 6900
Publisher
ROYAL SOC CHEMISTRY
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. © The Royal Society of Chemistry
URI
https://pr.ibs.re.kr/handle/8788114/2232
ISSN
2041-6520
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > Journal Papers (저널논문)
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