Unveiling the reaction mechanism of the das/chechik/marek synthesis of stereodefined quaternary carbon centers

Silva, Pedro J.; Bernardo, Carlos E. P.

http://hdl.handle.net/10284/9947

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Authors

Silva, Pedro J.

Bernardo, Carlos E. P.

Abstract(s)

The reaction mechanism of the Cu+‐catalyzed introduction of two all‐carbon‐substituted stereocenters in an ynamide system using a Grignard reagent, a zinc carbenoid, and an aldehyde, was investigated using density‐functional theory. In contrast to the formation of an organocopper(I) compound and subsequent carbocupration reaction, previously postulated as the initial step, the reaction proved to instead proceed through an initial complexation of the substrate alkyne bond by the Cu+‐catalyst, which primes this bond for reaction with the Grignard reagent. Subsequent addition of the zinc carbenoid then enables the nucleophilic attack on the incoming aldehyde, which is revealed as the rate‐limiting step. Our computations have also identified the factors governing the regio‐ and setereoselectivity of this interesting reaction, and suggest possible paths forits further development.

Keywords

Carbocupration Reaction mechanism DFT Zinc carbenoid Stereochemistry determinants

URI

http://hdl.handle.net/10284/9947

Citation

Silva, P.J.; Bernardo, C.E.P. (2021). Unveiling the Reaction Mechanism of the Das/Chechik/Marek Synthesis of Stereodefined Quaternary Carbon Centers. Applied Sciences 11 (11). DOI 10.3390/app11115002. EISSN 2076-3417.