SILICON IN SYNTHESIS .14. (METHOXY(TRIMETHYLSILYL)METHYL)LITHIUM - A NEW REAGENT FOR CARBONYL HOMOLOGATION
SILICON IN SYNTHESIS .14. (METHOXY(TRIMETHYLSILYL)METHYL)LITHIUM - A NEW REAGENT FOR CARBONYL HOMOLOGATION
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DOI：
10.1021/om00063a027
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发表时间：
1982-01-01
期刊：
影响因子：
2.8
通讯作者：
ROY, G
中科院分区：
文献类型：
--
作者：
MAGNUS, P;ROY, G
MeS R2 金属是锂，因为这些试剂的合成最常涉及使用烷基锂作为碱的氢-金属交换（方案 I）。已经描述了该金属化过程的各种变化，其中所得物质 1 通常用醛或酮处理，得到 α/3-烷氧基硅烷 2.3 加合物 2 或者经历三甲基硅烷醇锂元素的原位顺式消除，得到烯烃，或者相当稳定并在后续步骤中消除为烯烃。因此，该反应（最常被称为 Peterson 反应）可被视为 Wittig 烯烃合成的硅版本。极其广泛的取代基 Z 使其成为一种极其灵活的制备官能化烯烃的方法。此外，锂物质 1 似乎更具亲核性
MeS R2 metal is lithium, since the synthesis of these reagents most frequently involves hydrogen-metal exchange using an alkyllithium as the base (Scheme I). A comprehensiverange of variations of this metalation process has been described, where the resulting species 1 usually is treated with either an aldehyde or a ketone to give a/3-alkoxysilane 2.3 The adduct 2 either undergoes in situ syn elimination of the elements of lithium tri-methylsilanolate to give an alkene or is reasonably stable and is eliminated to an alkene in a subsequent step. As such, this reaction, most frequently known as the Peterson reaction, may be viewed as a silicon version of the Wittig olefin synthesis. The exceptionally wide range of sub-stituents Z make this an extremely flexible method of preparing functionalized alkenes. Furthermore, the lith-ium species 1 appear to be considerably more nucleophilic