Fleming F F, Shook B C, Jiang T, Steward O W
Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282, USA.
Org Lett. 1999 Nov 18;1(10):1547-50. doi: 10.1021/ol990854s.
[formula: see text] beta-Siloxy unsaturated nitriles are excellent precursors to enolate and nitrile anions that cyclize to cis- and trans-decalins, respectively. The stereoelectronic requirements of endocyclic enolates and exocyclic nitrile anions are complementary, providing cis- and trans-decalins from a common intermediate. This cyclization allows the synthesis of diastereomeric cis- and trans-decalins containing a contiguous array of quaternary-tertiary-quaternary stereocenters.
[化学式：见正文]β-硅氧基不饱和腈是烯醇负离子和腈负离子的优良前体，它们分别环化生成顺式和反式十氢化萘。内烯醇负离子和外环腈负离子的立体电子要求是互补的，可从共同中间体得到顺式和反式十氢化萘。这种环化反应能够合成含有连续季碳-叔碳-季碳立体中心排列的非对映异构顺式和反式十氢化萘。
