Synthesis of cyclic alkenylsiloxanes by semihydrogenation: a stereospecific route to (Z)-alkenyl polyenes.
Synthesis of cyclic alkenylsiloxanes by semihydrogenation: a stereospecific route to (Z)-alkenyl polyenes.
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DOI：
10.1002/chem.201403255
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发表时间：
2014-07-07
期刊：
影响因子：
--
通讯作者：
Anderson EA
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文献类型：
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作者：
Elbert BL;Lim DS;Gudmundsson HG;O'Hanlon JA;Anderson EA
环烯基硅氧烷是由炔基硅烷半加氢合成的，这是一个以前立体选择性差的反应。硅烷可以在多图尺度上合成，通过Hiyama-Denmark偶联得到生物活性天然产物中的(Z)-烯基多烯基序。硅烷的环大小是至关重要的：五元环硅氧烷在无氟条件下也偶联，而它们的六元同系物则不会，从而使该结构基序内的正交性成为可能。
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.