Chemoselective Carbonyl Allylations with Alkoxyallylsiletanes.
Chemoselective Carbonyl Allylations with Alkoxyallylsiletanes.
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烷氧基烯丙基硅烷的化学选择性羰基烯丙基化。
DOI：
10.1021/acs.joc.8b03028
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发表时间：
2019
期刊：
影响因子：
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通讯作者：
O'Neil,GregoryW
中科院分区：
文献类型：
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作者：
Spaltenstein,Paul;Cummins,ElizabethJ;Yokuda,Kelly-Marie;Kowalczyk,Tim;Clark,TimothyB;O'Neil,GregoryW
烷氧基烯丙基硅烷能够高度化学选择性和非对映选择性羰基烯丙基硅烷化。反应性底物包括水杨醛和乙醛酸。这些反应中的化学选择性被认为是由涉及首先将硅上的烷氧基与底物羟基交换，然后通过刘易斯酸性硅烷活化附近的羰基和分子内烯丙基化的机制引起的。以这种方式，含有多个反应性羰基的底物（例如，二醛或三酮）可以选择性地单烯丙基化，甚至克服固有的亲电性偏差。
Alkoxyallylsiletanes are capable of highly chemo- and diastereoselective carbonyl allylsilylations. Reactive substrates include salicylaldehydes and glyoxylic acids. Chemoselectivity in these reactions is thought to arise from a mechanism involving first exchange of the alkyoxy group on silicon with a substrate hydroxyl followed by activation of a nearby carbonyl by the Lewis acidic siletane and intramolecular allylation. In this way, substrates containing multiple reactive carbonyl groups (e.g., dialdehyde or triketone) can be selectively monoallylated, even overcoming inherent electrophilicity bias.