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분자활성 촉매반응 연구단
분자활성 촉매반응 연구단
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Regiodivergent Conjugate Addition Controlled by Rhodium(I) and Palladium(II) Catalysts: A Combined Computational and Experimental Study

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Title
Regiodivergent Conjugate Addition Controlled by Rhodium(I) and Palladium(II) Catalysts: A Combined Computational and Experimental Study
Author(s)
Hoimin Jung; Ansoo Lee; Jin Kim; Hyunwoo Kim; Mu-Hyun Baik
Publication Date
2017-09
Journal
ADVANCED SYNTHESIS & CATALYSIS, v.359, no.18, pp.3160 - 3175
Publisher
WILEY-V C H VERLAG GMBH
Abstract
A new divergent catalytic method for the 1,4- and 1,6-selective conjugate additions of arylboronic acids to α,β,γ,δ-unsaturated imino esters mediated by two different transition metal systems was developed. The rhodium complex carrying briphos, a new bicyclic, bridgehead phosphoramidite ligand, showed excellent regioselectivity towards 1,4-addition with product ratios of >50:1, whereas the palladium catalyst Pd(OPiv)2 reversed the regiochemistry to afford the 1,6-product with mild levels of selectivity of ≈1:7. Both theoretical and experimental studies were utilized to understand the catalytic systems and to elucidate the molecular level mechanism leading to the selective reactions. Since Rh(I) and Pd(II) are both d8-complexes, their electronic structures and binding behaviours can be compared. Our calculations suggest that the outcome of the catalysis in the Rh(I) system is under kinetic control, where the migratory insertion of the alkene is the step that determines the regiochemistry. When the Pd(II) catalyst is used, the regiochemistry is under thermodynamic control where the relative stability of the η3-π-allyl- over the η3-aza-π-allyl-intermediate dictates the selectivity at the 1,6-migratory insertion step. (Figure presented.). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinhei
URI
https://pr.ibs.re.kr/handle/8788114/3979
ISSN
1615-4150
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > Journal Papers (저널논문)
Center for Nanomaterials and Chemical Reactions(나노물질 및 화학반응 연구단) > Journal Papers (저널논문)
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