Allyltrichlorosilane

Kočovský, Pavel

doi:10.1002/047084289x.rn00568

Cited by 1 publication

(1 citation statement)

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“…The resultant products can be further utilized for the synthesis of natural products, pharmaceuticals, agrochemicals, polymers, and catalysis. 1,2 Conventional syntheses of this important motif involve metal-catalyzed cross-couplings of activated arenes (Ar -X and Ar -M). 3,4 These coupling reactions require several prefunctionalizaton steps that are intrinsically necessary to achieve reactivity and which also control regio-and chemoselectivity.…”

Section: Introductionmentioning

confidence: 99%

Chromium-Salen Catalyzed Cross-Coupling of Phenols: Mechanism and Origin of the Selectivity

et al. 2019

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A highly chemoselective phenol cross-coupling reaction catalyzed by a Cr-salen catalyst was developed. Kinetic studies showed that the oxidation of Cr(III) to Cr(V) is the rate-determining step of the reaction. In addition, experimental stoichiometric analysis showed that a high valentCr(V) specie is the active catalyst for this process. The selectivity of the reaction was found to be determined by the cross-coupling carbon-carbon bond forming reaction, rather than any precoordination species. It appears that the lowest energy cross-coupling pathway requires a lesser degree of electronic reorganization in its transition state vs the lowest energy homo-coupling pathway. This result was supported by stoichiometric Cr(V) kinetics, 13 C kinetic isotope effects, and DFT calculations. The understanding of the full landscape of this reaction, allowed us to develop a general analysis to predict the regioselectivity of the cross-coupling reaction.

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Section: Introductionmentioning

confidence: 99%