Allylic Alkylation Catalyzed by Molybdenum Complexes Containing Polydentate Phosphinoalkyl-Silyl Ligands

Minato, Makoto; Naoto Wada; Takefumi Katsuren; Hiroaki Shu

doi:10.51094/jxiv.18

##article.authors##

Minato, Makoto Yokohama National University, Department of Materials Chemistry, Graduate School of Engineering https://orcid.org/0000-0002-5151-7443
Naoto Wada Yokohama National University, Department of Materials Chemistry, Graduate School of Engineering
Takefumi Katsuren Yokohama National University, Department of Materials Chemistry, Graduate School of Engineering
Hiroaki Shu Yokohama National University, Department of Materials Chemistry, Graduate School of Engineering

DOI:

https://doi.org/10.51094/jxiv.18

キーワード:

high regioselectivity、 Tsuji-Trost reaction、 trans-influence

抄録

The reaction of allyl alcohol derivatives with soft carbon nucleophiles, such as dimethyl sodiomalonate, in the presence of catalytic quantities of silyl-molybdenum hydrido complexes ([MoH3{Si(R)[Ph2PCH2CH2P(Ph)C6H4-o]2}] or [MoH3([Ph2PCH2CH2P(Ph)C6H4-o]R2Si-P,P,Si)]) is probed. The regioselectivity of the reaction and the catalyst activity were found to be highly dependent on the solvents used. With trisubstituted double bond olefins, the products alkylated at the unsubstituted allylic terminus were obtained in 95-99% selectivity. This regioselectivity is complementary to the Ir-catalyzed reactions, in which highly regioselective alkylation at the substituted allylic terminus was achieved. Direct conversion of allylic alcohol was also examined. The reaction of ethylbenzenesulfonylacetate or diethyl malonate proceeds under neutral conditions without addition of bases from outside.

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