Synthesis of 2-chloro-2-imidoylaziridines via aza-darzens-type reaction of 3,3-dichloro-1-azaallylic anions and N-(arylsulfonyl) imines
Synthesis of 2-chloro-2-imidoylaziridines via aza-darzens-type reaction of 3,3-dichloro-1-azaallylic anions and N-(arylsulfonyl) imines
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DOI：
10.1021/jo060241a
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发表时间：
2006-08-04
影响因子：
3.6
通讯作者：
De Kimpe, Norbert
中科院分区：
文献类型：
--
作者：
Giubellina, Nicola;Mangelinckx, Sven;De Kimpe, Norbert
通过用二异丙基氨基锂使α，α-二氯酮亚胺10去质子化而产生的3，3-二氯-1-氮杂烯丙基阴离子与N-磺酰基醛亚胺7反应，产生曼尼希型产物N-[2，2-二氯-3-（N-烷基亚氨基）-1，3-二芳基丙基]苯磺酰胺11。后者的稳定化合物在亚氨基官能团处水解，以优异的产率得到N-[2，2-二氯-3-氧代-1，3-二芳基丙基]苯磺酰胺12。N-[2，2-二氯-3-（N-烷基亚氨基）-1，3-二芳基丙基]苯磺酰胺11环化为顺式-3-芳基-2-氯-2-亚氨基氮杂环丙烷19，产率为81-99%，具有高的非对映选择性，代表了一类新的且容易获得的稳定的2-氯氮杂环丙烷。最后，由顺式-3-芳基-2-氯-2-亚胺基氮杂环丙烷19和氰基硼氢化钠在乙酸存在下的反应，得到高度立体选择性的2-（氨甲基）-2-氯氮杂环丙烷27（产率70-98%; de > 95-99）。后者2-（氨甲基）氮杂环丙烷27代表立体化学定义的小氮杂环，其在文献中几乎没有报道。
3,3-Dichloro-1-azaallylic anions, generated by deprotonation of alpha, alpha-dichloroketimines 10 with lithium diisopropylamide, reacted with N-sulfonylaldimines 7 to produce the Mannich-type products N-[2,2-dichloro-3-(N-alkylimino)-1,3-diarylpropyl] benzenesulfonamides 11. The latter stable compounds were hydrolyzed at the imino functionality to afford N-[2,2-dichloro-3-oxo-1,3-diarylpropyl] benzenesulfonamides 12 in excellent yields. N-[2,2-Dichloro-3-(N-alkylimino)-1,3-diarylpropyl] benzenesulfonamides 11 were cyclized to cis-3-aryl-2-chloro-2-imidoylaziridines 19 in 81-99% yield with high diastereoselectivity, representing a novel and readily available class of stable 2-chloroaziridines. Finally, a highly stereoselective entry to 2-(aminomethyl)-2-chloroaziridines 27 (70-98% yield; de > 95-99) was worked out from the reaction of cis-3-aryl-2-chloro-2-imidoylaziridines 19 and sodium cyanoborohydride in the presence of acetic acid. The latter 2-(aminomethyl) aziridines 27 represent stereochemically defined small azaheterocyclic rings which were scarcely reported in the literature.