GENERATION AND SYNTHETIC APPLICATIONS OF 2-LITHIO-1,3-DITHIANES
GENERATION AND SYNTHETIC APPLICATIONS OF 2-LITHIO-1,3-DITHIANES
复制标题
DOI：
10.1021/jo00890a018
复制
发表时间：
1975-01-01
影响因子：
3.6
通讯作者：
COREY, EJ
中科院分区：
文献类型：
--
作者：
SEEBACH, D;COREY, EJ
1，3-二噻烷的制备和金属化导致保护的酰基锂衍生物，其在合成上等同于酰基阴离子。给出了2-锂-1，3-二噻烷与常见亲电试剂如烷基、烯丙基和苄基卤化物、醛、酮和羧酸衍生物以及1，2-和1，3-氧化物反应的实验步骤和一些实例。本文列举的例子表明了2-锂-1，3-二噻烷的高度亲核性及其在合成中的应用价值，现代有机合成的主要目标之一是拓宽碳原子和官能团的组装技术。为了增加开发合成复杂分子的简单途径的可能性，需要具有相反极性的试剂以引入给定的片段或合成子。因此，亲核氰化物CM-或亲电二氧化碳CO 2可用于将合成子考克斯掺入分子中。我们认为，设计新的试剂，即不可能的亲核试剂或亲电试剂的等价物，是扩展有机化学一般方法学的有效策略。
The preparation and metalation of 1, 3-dithianes leads to protected acyllithium derivatives which are synthetically equivalent to acyl anions. Experimental proceduresand a number of examples are given for the reactions of 2-lithio-l, 3-dithianes with common electrophiles such as alkyl, allyl, and benzyl halides, aldehydes, ketones, and carboxylic acid derivates, as well as 1, 2-and 1, 3-oxides. The examples given demonstrate the highnucleophilicity of 2-lithio-l, 3-dithianes and the value of these reagents in synthesis.One of the majorobjectives of modernorganic synthesis is the broadening of techniques for assembling collections of carbon atoms and functional groups. In orderto increase the probability of developing simple routes for the synthe-sis of complex molecules, it is desirable to have reagents of opposite polarity for the introduction of a given fragment or synthon. 1 Thus, the nucleophilic cyanide, CM-, or the electrophilic carbon dioxide, CO2, can be used for incorpo-rating the synthon COX into a molecule. We consider the design of new reagents which are the equivalents of inac-cessible nucleophiles or electrophiles an effective strategy for the extension of the general methodology of organic