Ueki Hisanori, Ellis Trevor K, Martin Collin H, Boettiger Tomas U, Bolene Shawna B, Soloshonok Vadim A
Department of Chemistry and Biochemistry, University of Oklahoma, Norman, Oklahoma 73019, USA.
J Org Chem. 2003 Sep 5;68(18):7104-7. doi: 10.1021/jo0301494.
A synthetically practical and operationally convenient method for preparing (S)-2-[N-(N'-benzylprolyl)amino]benzophenone (BPBP) and hitherto unknown (S)-2-[N-(N'-benzylprolyl)amino]-4-methylbenzophenone (4-Me-BPBP), (S)-2-[N-(N'-benzylprolyl)amino]-5-nitrobenzophenone (5-NO(2)-BPBP), and their corresponding Ni(II) complexes with glycine [GlyNi(II)BPBP], a widely used chiral equivalent of nucleophilic glycine, and new analogues [GlyNi(II)-4-Me-BPBP] and [GlyNi(II)-5- NO(2)-BPBP] is described. The key step of the method is the synthetically efficient amid bond formation between the corresponding o-aminobenzophenones, featuring significant steric shielding and low nucleophilicity of the amino functionality as well as sterically constrained (S)-N-benzylproline (BP).
一种合成实用且操作简便的方法，用于制备（S）-2-[N-（N'-苄基脯氨酰基）氨基]二苯甲酮（BPBP）以及迄今未知的（S）-2-[N-（N'-苄基脯氨酰基）氨基]-4-甲基二苯甲酮（4-Me-BPBP）、（S）-2-[N-（N'-苄基脯氨酰基）氨基]-5-硝基二苯甲酮（5-NO₂-BPBP），及其与甘氨酸形成的相应镍（II）配合物[甘氨酸镍（II）BPBP]，一种广泛使用的亲核甘氨酸手性等价物，以及新的类似物[甘氨酸镍（II）-4-Me-BPBP]和[甘氨酸镍（II）-5-NO₂-BPBP]。该方法的关键步骤是在相应的邻氨基二苯甲酮之间进行合成高效的酰胺键形成，其特征在于氨基官能团具有显著的空间屏蔽和低亲核性，以及空间受限的（S）-N-苄基脯氨酸（BP）。
