通过2,3-环氧环烷醇的非羟醛缩合重排反应简便合成顺式-2-烷基-3-三烷基硅氧基环烷酮。
Facile synthesis of cis-2-Alkyl-3-trialkylsilyloxycycloalkanones via the non-aldol aldol rearrangement of 2,3-epoxycycloalkanols.
作者信息
Jung Michael E, Allen Damian A
机构信息
Department of Chemistry and Biochemistry, University of California, Los Angeles, 405 Hilgard Avenue, Los Angeles, California 90095, USA.
出版信息
Org Lett. 2008 May 15;10(10):2039-41. doi: 10.1021/ol800423m. Epub 2008 Apr 23.
Silyl triflate-promoted rearrangement of cis-2,3-epoxycycloalkanols A, prepared by epoxidation of the cyclic allylic alcohol and then silylation, afforded good yields ( approximately 70-75%) of the cis-2-alkyl-3-silyloxycycloalkanones B, presumably via the intermediates C and D, even with quite large alpha-substituents, e.g., tert-butyl. Finally, it has been shown that the stereochemistry of the epoxy alcohol is crucial as one would expect from the mechanism.
通过环烯丙醇环氧化然后硅烷化制备的顺式-2,3-环氧环烷醇A，在三氟甲磺酸硅促进下重排，即使对于相当大的α-取代基，例如叔丁基，也能以良好的产率（约70-75%）得到顺式-2-烷基-3-硅氧基环烷酮B，推测是通过中间体C和D实现的。最后，正如从机理中所预期的那样，已表明环氧醇的立体化学至关重要。
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