α-（N-甲酰基）烷基铜酸盐与炔丙基底物的反应：α-氨基丙二烯和Δ3-吡咯啉的合成路线
Reaction of alpha-(N-carbamoyl)alkylcuprates with propargyl substrates: synthetic route to alpha-amino allenes and delta3-pyrrolines.
作者信息
Dieter R Karl, Chen Ningyi, Yu Huayun, Nice Lois E, Gore Vinayak K
机构信息
Department of Chemistry, Howard L. Hunter Laboratory, Clemson University, Clemson, South Carolina 29634-0973, USA.
出版信息
J Org Chem. 2005 Mar 18;70(6):2109-19. doi: 10.1021/jo0481405.
[reaction: see text] Carbamate deprotonation followed by treatment with CuCN.2LiCl affords alpha-(N-carbamoyl)alkylcuprates which react with propargyl halides, mesylates, tosylates, phosphates, acetates, and epoxides to give alpha-(N-carbamoyl) allenes via an anti-S(N)2' substitution process. Propargyl halides, sulfonates, and phosphates give good yields of carbamoyl allenes, while the acetates afford low yields. Propargyl substrates undergo regiospecific S(N)2' substitution in the absence of severe steric hindrance. The alpha-(N-carbamoyl) allenes can be cyclized to 2-oxazolidinones or deprotected to afford the free amines which can be cyclized to Delta(3)-pyrrolines with either AgNO(3) or Ru(3)(CO)(12).
[反应：见正文] 氨基甲酸酯去质子化，然后用CuCN·2LiCl处理，得到α-(N-氨基甲酰基)烷基铜酸盐，其与炔丙基卤化物、甲磺酸盐、对甲苯磺酸盐、磷酸盐、乙酸酯和环氧化物反应，通过反S(N)2'取代过程生成α-(N-氨基甲酰基)丙二烯。炔丙基卤化物、磺酸盐和磷酸盐能以良好的产率得到氨基甲酰基丙二烯，而乙酸酯的产率较低。在没有严重空间位阻的情况下，炔丙基底物会发生区域特异性的S(N)2'取代反应。α-(N-氨基甲酰基)丙二烯可以环化生成2-恶唑烷酮，或者脱保护得到游离胺，游离胺可以用AgNO(3)或Ru(3)(CO)(12)环化生成Δ(3)-吡咯啉。
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