A convergent fragment coupling strategy to access quaternary stereogenic centers.

Kerkovius, Jeff K; Wong, Alice R; Mak, Victor W; Reisman, Sarah E

Kerkovius, Jeff K; Wong, Alice R; Mak, Victor W; Reisman, Sarah E.

Afiliación

Kerkovius JK; The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology Pasadena California 91125 USA reisman@caltech.edu.
Wong AR; The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology Pasadena California 91125 USA reisman@caltech.edu.
Mak VW; The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology Pasadena California 91125 USA reisman@caltech.edu.
Reisman SE; The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology Pasadena California 91125 USA reisman@caltech.edu.

Chem Sci ; 14(16): 4397-4400, 2023 Apr 26.

Article en En | MEDLINE | ID: mdl-37123185

RESUMEN

The formation of quaternary stereogenic centers via convergent fragment coupling is a longstanding challenge in organic synthesis. Here, we report a strategy for the formation of quaternary stereogenic centers in polycyclic systems based upon the semi-pinacol reaction. In the key transformation, two fragments of a similar size and complexity are joined by a 1,2-addition of an alkenyl lithium to an epoxy ketone, and the resulting epoxy silyl ether undergoes a semi-pinacol rearrangement catalyzed by N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide (TMSNTf2) or trimethylsilyl trifluoromethanesulfonate (TMSOTf). Polycyclic scaffolds were generated in high yields and the reaction conditions tolerated a variety of functional groups including esters, silyl ethers, enol ethers, and aryl triflates. This method provides a useful strategy for the synthesis of complex polycyclic natural product-like scaffolds with quaternary stereogenic centers from simplified fragments.

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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Chem Sci Año: 2023 Tipo del documento: Article Pais de publicación: Reino Unido

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