Preparation and Reactivity of Allyl N-[(Arylsulfonyl)oxy]carbamates, New Reagents for Electrophilic Transfer of an NHAlloc Group
Preparation and Reactivity of Allyl N-[(Arylsulfonyl)oxy]carbamates, New Reagents for Electrophilic Transfer of an NHAlloc Group
复制标题
N-[(芳基磺酰基)氧基]氨基甲酸烯丙酯的制备和反应活性，NHAlloc基团亲电转移新试剂
DOI：
10.1021/jo00126a062
复制
发表时间：
1995
影响因子：
3.6
通讯作者：
J. Genêt
中科院分区：
文献类型：
--
作者：
C. Greck;L. Bischoff;F. Ferreira;J. Genêt
碳-氮键通常是由亲核氮攻击带有离去基的亲电碳，通过sn2型反应形成的。自从Sheverdina和Kocheskov发现极性反转过程以来，加上新的金属化方法的发展，人们越来越关注开发亲核碳胺化试剂的亲电试剂。2这种“Umpolung”胺化工艺也被改进为通过亲电胺化试剂与手性烯醇化物反应来构建手性胺。最近，Oppolzer等人报道了一种手性氯-亚硝基试剂，它与前手性酮烯醇酯反应，具有高度的对映面分化。氮保护胺也是重要的合成中间体，新的胺化试剂允许一步转移一个氮保护的部分将是极大的兴趣。我们最近报道了用亲电胺化剂，金属化的ii -butyl N-(tosyloxy)氨基甲酸酯处理各种有机金属，可以形成胺，其ii -butyl氨基甲酸酯产量良好至中等。由Collet等人描述的2V-Boc-3-（4-氰苯基）恶氮吡啶也被证明是一种有效的亲电胺化剂。6 Ricci等人开发了lV， 0-二（三甲基硅基）羟胺，该羟胺与高阶芳基铜酸盐反应后传递NHSiMe3片段，水解后产生相应的游离芳胺。然而，使用酸性条件去除氨基甲酸乙酯丁酯（Boc）的功能使其
Carbon-nitrogen bonds are usually formed by attack of nucleophilic nitrogen on an electrophilic carbon bearing a leaving group, via an SN2-type reaction. Since the discovery of the polarity reversal process by Sheverdina and Kocheskov, 1 in combination with thedevelopment of new metalation procedures, increased attention has been focused on the development of electrophilic reagents for the amination of carbon nucleophiles. 2 This type of “Umpolung” amination process has also been modified for the construction of chiral amines by the reaction of electrophilic aminating reagents with chiral enolates. 3 More recently, Oppolzer et al. have reported a chiral-chloro-a-nitroso reagent whichreacted with prochiral ketone enolates with high enantiofacial differentiation. 4 N-Protected amines are also important as synthetic intermediates, and new aminating reagents that allow the one step transfer of an N-protected moiety would be of great interest. We-recently reported that treatment of various organometallics with the electrophilic aminat-ing agent, metalated ieri-butyl N-(tosyloxy) carbamate, resulted in the formation of amines as their ieri-butyl carbamates in good to moderate yields. 5 2V-Boc-3-(4-cyanophenyl) oxaziridine, described by Collet et al., has also been shown to be an effective electrophilic aminating agent. 6 Ricci et al. havedeveloped lV, 0-bis (trimethylsilyl) hydroxylamine whichupon reaction with high order aryl cuprates delivers the NHSiMe3 moiety to produce, after hydrolysis, the correspondingfree aromatic amines. 7 However, the use of acidic conditionsfor the removal of the ieri-butyl carbamate (Boc) functionality renders it