AMELIORATION OF THE CONJUGATE ADDITION CHEMISTRY OF ALPHA-ALKOXYCOPPER REAGENTS - APPLICATION TO THE STEREOSPECIFIC SYNTHESIS OF C-GLYCOSIDES
AMELIORATION OF THE CONJUGATE ADDITION CHEMISTRY OF ALPHA-ALKOXYCOPPER REAGENTS - APPLICATION TO THE STEREOSPECIFIC SYNTHESIS OF C-GLYCOSIDES
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DOI：
10.1021/ja00250a029
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发表时间：
1987-08-05
影响因子：
15
通讯作者：
FUCHS, PL
中科院分区：
文献类型：
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作者：
HUTCHINSON, DK;FUCHS, PL
（（苄氧基）甲基）-和[（（四氢吡喃-2-基）氧基）甲基]锂试剂通过相应的α-环戊二烯基的金属转移来合成。烷氧基锡烷。这些锂试剂转化成许多有机铜试剂，并检查它们与三种不同空间需求的烯酮的反应性。详细研究了铜（I）前体以及添加剂如三氟化硼醚合物和三甲基氯硅烷的影响。这种技术的一对异构体的三-正丁基锡烷基吡喃葡萄糖苷的应用揭示了通过共轭加成反应的立体定向合成的C-糖苷的烯酮的范围和限制。
((Benzyloxy)methyl)- and [((tetrahydropyran-2-yl)oxy)methyl]lithium reagents were synthesized via transmetalation of the corresponding .alpha.-alkoxystannanes. These lithium reagents were converted into a number of organocopper reagents, and their reactivity with three enones of differing steric demand was examined. The effect of copper(I) precursor as well as additives such as boron trifluoride etherate and chlorotrimethylsilane was examined in detail. Application of this technology to a pair of isomeric tri-n-butylstannyl glucopyranosides reveals the scope and limitations for the stereospecific synthesis of C-glycosides via conjugate addition reactions to enones.