STANNYLATION-DESTANNYLATION - PREPARATION OF ALPHA-ALKOXY ORGANOLITHIUM REAGENTS AND SYNTHESIS OF DENDROLASIN VIA A CARBINYL CARBANION EQUIVALENT
STANNYLATION-DESTANNYLATION - PREPARATION OF ALPHA-ALKOXY ORGANOLITHIUM REAGENTS AND SYNTHESIS OF DENDROLASIN VIA A CARBINYL CARBANION EQUIVALENT
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DOI：
10.1021/ja00473a025
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发表时间：
1978-01-01
影响因子：
15
通讯作者：
STILL, WC
中科院分区：
文献类型：
--
作者：
STILL, WC
三丁基锡基锂（1）是一种用于制备含氧有机锂试剂的有价值的试剂，并且易于通过二异丙基氨基锂与三丁基锡氢化物的去质子化来制备。将I加成到烷基或芳基醛上，得到羟基锡烷（RCH（OH）Sn（Bu）3），然后用氯乙基乙醚保护，得到乙氧基乙基衍生物（II），产率> 90%。用丁基锂处理，II产生相应的烷氧基有机锂试剂（RCH（OR '）Li）。这些试剂在合成上可用作原基碳负离子等价物。以呋喃-3-甲醛为起始原料合成Dendrolasin和（±）-9-羟基Dendrolasin为例，说明了新有机锂试剂在天然产物合成中的应用。
Tributylstannyllithium (1) is a valuable reagent for the preparation of oxyfunctional organolithium reagents and is readily prepared by deprotonation of tributyltin hydride with lithium diisopropylamide. Addition of I to an alkyl or aryl aldehyde yields an-hydroxystannane (RCH (OH) Sn (Bu) 3) which is then protected with-chloroethyl ethyl ether to give the ethoxyethyl derivative (II) in> 90% yield. On treatment with butyllithium, II yields the corresponding-alkoxy organolithium reagent (RCH (OR') Li). These reagents are synthetically useful as carbinyl carbanion equivalents. Application of the new or-ganolithium reagents to natural product synthesis is illustrated by a simple synthesis of dendrolasin and (±)-9-hydroxydendro-lasin from furan-3-carboxaldehyde.