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Synthesis of angularly substituted trans-fused hydroindanes by convergent coupling of acyclic precursors.

ABSTRACT: Angularly substituted trans-fused hydroindanes are now accessible by the direct and convergent union of trimethylsilyl (TMS)-alkynes with 4-hydroxy-1,6-enynes by a process that forges three C-C bonds, one C-H bond, and two new stereocenters. The annulation is proposed to proceed by initial formation of a Ti-alkyne complex (with a TMS-alkyne) followed by regioselective alkoxide-directed coupling with the enyne, stereoselective intramolecular cycloaddition, elimination of phenoxide, 1,3-metallotropic shift, and stereoselective protonation of the penultimate allylic organometallic intermediate. Several examples are given to demonstrate the compatibility of this reaction with substrates bearing aromatic and aliphatic substituents, and an empirical model is presented to accompany the stereochemical observations.

SUBMITTER: Jeso V

PROVIDER: S-EPMC4063191 | biostudies-literature | 2014 Jun

REPOSITORIES: biostudies-literature

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Synthesis of angularly substituted trans-fused hydroindanes by convergent coupling of acyclic precursors.

Jeso Valer V Aquino Claudio C Cheng Xiayun X Mizoguchi Haruki H Nakashige Mika M Micalizio Glenn C GC

Journal of the American Chemical Society 20140529 23

Angularly substituted trans-fused hydroindanes are now accessible by the direct and convergent union of trimethylsilyl (TMS)-alkynes with 4-hydroxy-1,6-enynes by a process that forges three C-C bonds, one C-H bond, and two new stereocenters. The annulation is proposed to proceed by initial formation of a Ti-alkyne complex (with a TMS-alkyne) followed by regioselective alkoxide-directed coupling with the enyne, stereoselective intramolecular cycloaddition, elimination of phenoxide, 1,3-metallotro ...[more]

PMID: 24856045

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