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

Valer Jeso, Claudio Aquino, Xiayun Cheng, Haruki Mizoguchi, Mika Nakashige, Glenn C. Micalizio

Research output: Contribution to journalArticle

20 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)8209-8212
Number of pages4
JournalJournal of the American Chemical Society
Volume136
Issue number23
DOIs
Publication statusPublished - Jun 11 2014
Externally publishedYes

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Bearings (structural)
Alkynes
Cycloaddition
Protonation
Organometallics
Substrates
Cycloaddition Reaction

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry
  • Medicine(all)

Cite this

Synthesis of angularly substituted trans-fused hydroindanes by convergent coupling of acyclic precursors. / Jeso, Valer; Aquino, Claudio; Cheng, Xiayun; Mizoguchi, Haruki; Nakashige, Mika; Micalizio, Glenn C.

In: Journal of the American Chemical Society, Vol. 136, No. 23, 11.06.2014, p. 8209-8212.

Research output: Contribution to journalArticle

Jeso, Valer ; Aquino, Claudio ; Cheng, Xiayun ; Mizoguchi, Haruki ; Nakashige, Mika ; Micalizio, Glenn C. / Synthesis of angularly substituted trans-fused hydroindanes by convergent coupling of acyclic precursors. In: Journal of the American Chemical Society. 2014 ; Vol. 136, No. 23. pp. 8209-8212.
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