3-取代环烷酮的软烯醇化反应表现出显著优于硬烯醇化条件的区域选择性。
Soft Enolization of 3-Substituted Cycloalkanones Exhibits Significantly Improved Regiocontrol vs Hard Enolization Conditions.
机构信息
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.
出版信息
Org Lett. 2021 Dec 17;23(24):9616-9619. doi: 10.1021/acs.orglett.1c03844. Epub 2021 Dec 6.
Abstract
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.
摘要
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。
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