Journal of Organic Chemistry
Journal of Organic Chemistry
4 years ago

Mechanistic Study of Nickel-Catalyzed Reductive Coupling of Ynoates and Aldehydes

Mechanistic Study of Nickel-Catalyzed Reductive Coupling of Ynoates and Aldehydes
Sanjeewa K. Rodrigo, Hairong Guan
In this work, (1,5-hexadiene)Ni(SIPr) (SIPr = 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene) is used in place of Ni(COD)2/SIPr·HBF4/KOtBu (COD = 1,5-cyclooctadiene) as a more robust catalyst for regioselective reductive coupling of ynoates and aldehydes with triethylsilane. The catalytic reaction of ethyl 3-(trimethylsilyl)propiolate and methyl 4-formylbenzoate shows first-order dependence on aldehyde and catalyst concentrations, inverse first-order dependence on [ynoate], and no dependence on [silane]. The kinetics data, coupled with deuterium-labeling experiments, support a mechanism involving dissociation of the ynoate from a catalytically dormant nickelacyclopentadiene intermediate prior to turnover-limiting formation of a catalytically active nickeladihydrofuran.

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b00483

DOI: 10.1021/acs.joc.7b00483

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