Enantiocontrolled Synthesis of Polychlorinated Hydrocarbon Motifs: A Nucleophilic Multiple Chlorination Process Revisited
Enantiocontrolled Synthesis of Polychlorinated Hydrocarbon Motifs: A Nucleophilic Multiple Chlorination Process Revisited
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DOI：
10.1021/jo802093d
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发表时间：
2009-01-16
影响因子：
3.6
通讯作者：
Tanaka, Tetsuaki
中科院分区：
文献类型：
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作者：
Yoshimitsu, Takehiko;Fukumoto, Naoya;Tanaka, Tetsuaki
多氯代烃基序已经通过手性环氧化物的亲核多重氯化以对映体纯的形式合成，其立体特异性地将卤素原子引入到含氧分子支架中。本研究证明了N-氯代琥珀酰亚胺（NCS）/有机膦试剂体系的范围，形成多个sp（3）C-Cl键在一个有规律的重复模式，具有适当的立体化学构型，并评估其适用性的各种环氧化物具有复杂的结构。值得注意的是，四氯化基序是通过使用NCS/Ph 3 P从二环氧化物一步制备的。此外，已发现与NCS组合使用的Ph 2 PCl充当NCS/Ph 3 P的潜在有用的替代物，特别是用于促进烯基取代的环氧化物的二氯化反应。
Polychlorinated hydrocarbon motifs have been synthesized in enantiomerically pure forms by means of nucleophilic multiple chlorinations of chiral epoxides, which stereospecifically incorporate halogen atoms into oxygenated molecular scaffolds. The present study demonstrates the scope of the N-chlorosuccinimide (NCS)/organophosphine reagent system that forms multiple sp(3)C-Cl bonds in a regularly repeating pattern, with proper stereochemical configurations and evaluates its applicability to various epoxides having elaborate structures. It is noteworthy that tetrachlorinated motifs are produced in one step from bisepoxides by using NCS/Ph3P. Furthermore, Ph2PCl used in combination with NCS has been found to serve as a potentially useful alternative to NCS/Ph3P, especially for promoting dichlorination reactions of alkenyl-substituted epoxides.