Department of Chemistry, University of California, Irvine, California 92697-2025, United States.
Department of Pharmaceutical Sciences, University of California, Irvine, California 92697-2025, United States.
Org Lett. 2021 Dec 17;23(24):9616-9619. doi: 10.1021/acs.orglett.1c03844. Epub 2021 Dec 6.
Soft enolization conditions are revealed to be markedly better than the typically applied hard enolization protocols for regioselective enoxysilane formation from unsymmetrical 3-substituted cycloalkanones. Five-, six-, and seven-membered cycloalkanones each with 3-methyl, 3-isopropyl, or 3-phenyl substituents were investigated, and in all but one case, regioselectivities were ≥11:1 for enolization away from the substituent. These results are complementary to the regiospecific enoxysilane formation derived from cycloalkenone conjugate addition/enolate silylation.
软烯醇化条件明显优于通常应用的硬烯醇化方法，可从非对称 3-取代环烷酮中高区域选择性地生成烯氧基硅烷。研究了具有 3-甲基、3-异丙基或 3-苯基取代基的五、六和七元环烷酮，除一种情况外，所有情况下烯醇化时远离取代基的区域选择性均≥11:1。这些结果与环烯酮共轭加成/烯醇硅烷化衍生的区域特异性烯氧基硅烷形成互补。
