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분자활성 촉매반응 연구단
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Head-to-Head Homocoupling of Ynamides via a Dual Activation Mode of Triple Bonds by Half-Sandwich Metal Complexes

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Title
Head-to-Head Homocoupling of Ynamides via a Dual Activation Mode of Triple Bonds by Half-Sandwich Metal Complexes
Author(s)
Manoj Kumar Sahoo; Sourav Pradhan; Dongwook Kim; Jung-Woo Park; Sukbok Chang
Publication Date
2022-04
Journal
Organometallics, v.41, no.7, pp.900 - 905
Publisher
American Chemical Society
Abstract
© 2022 American Chemical Society.Reported herein is the half-sandwich Rh-mediated head-to-head homocoupling of terminal ynamides to furnish dienyl bisamido rhodacyclic complexes, where the Rh-vinyl bond was formed selectively at the α-carbon to the nitrogen atom. This transformation was extended to include piano-stool Ru and Ir complexes to display an analogous homocoupling reactivity. Based on density functional theory studies, the reaction was proposed to proceed via a dual activation mode of the ynamide triple bonds: (i) generation of a zwitterionic keteniminyl metal species to induce an intramolecular chloride transfer and (ii) syn-carbometallation of the second coordinated alkynes by the alkenyl metal intermediate. An oxidative transformation of the homocoupled metal complexes gave multifunctional dienyl bisamide compounds.
URI
https://pr.ibs.re.kr/handle/8788114/11431
DOI
10.1021/acs.organomet.2c00073
ISSN
0276-7333
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > 1. Journal Papers (저널논문)
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