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Synthesis of Cyclic Alkenylsiloxanes by Semihydrogenation: A Stereospecific Route to ( Z )‐Alkenyl Polyenes
Author(s) -
Elbert Bryony L.,
Lim Diane S. W.,
Gudmundsson Haraldur G.,
O'Hanlon Jack A.,
Anderson Edward A.
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201403255
Subject(s) - polyene , silanes , chemistry , silane , stereospecificity , stereoselectivity , ring (chemistry) , stereochemistry , polymer chemistry , combinatorial chemistry , organic chemistry , catalysis
Cyclic alkenylsiloxanes were synthesized by semihydrogenation of alkynylsilanes—a reaction previously plagued by poor stereoselectivity. The silanes, which can be synthesized on multigram scale, undergo Hiyama–Denmark coupling to give ( Z )‐alkenyl polyene motifs found in bioactive natural products. The ring size of the silane is crucial: five‐membered cyclic siloxanes also couple under fluoride‐free conditions, whilst their six‐membered homologues do not, enabling orthogonality within this structural motif.