Sequential ring-closing metathesis/Pd-catalyzed, Si-assisted cross-coupling reactions: General synthesis of highly substituted unsaturated alcohols and medium-sized rings containing a 1,3-cis-cis diene unit

Scott E. Denmark, Shyh Ming Yang

Research output: Contribution to journalArticle

Abstract

A sequential ring-closing metathesis/silicon-assisted cross-coupling protocol has been developed. Alkenyldimethylsilyl ethers of allylic, homoallylic and bis(homoallylic) alcohols undergo facile ring closure with Schrock's catalyst to afford 5-, 6-, and 7-membered cycloalkenylsiloxanes, respectively, in some cases with substituents on both alkenyl carbons. These siloxanes are highly effective coupling partners that afford styrenes and dienes (with various aryl and alkenyl halides) in high yield and specificity as well as good functional group compatibility. The siloxanes bearing a Z-iodoalkenyl tether undergo an intramolecular coupling process in the presence of [allylPdCl] 2 which constitutes a powerful method for the construction of medium-sized rings with an internal 1,3-cis-cis diene unit. The formation of 9-, 10-, 11-, and 12-membered carbocyclic dienes is achieved in good yield. Extension to the synthesis of 9-membered ring unsaturated ethers has also been accomplished. Noteworthy features of this process include: (1) highly stereospecific intramolecular coupling, (2) flexible positioning of the revealed hydroxy group, and (3) potential extension to other medium-sized carbocycles and heterocycles. Graphical Abstract.

Original languageEnglish (US)
Pages (from-to)9695-9708
Number of pages14
JournalTetrahedron
Volume60
Issue number43 SPEC. ISS.
DOIs
StatePublished - Oct 18 2004

Keywords

  • Cross-coupling
  • Medium-sized ring
  • Organosilicon
  • Palladium
  • RCM

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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