基于PPM的氨基酸型两性水溶性手性膦配体前体的合成

基于手性膦配体(2S,4S)-2-二苯膦甲基-4-二苯膦基四氢吡咯(PPM)合成了一种新型的氨基酸型两性水溶性手性膦配体的前体。首先以(2S,4S)-N-Boc-2-对甲苯磺酰氧甲基-4-对甲苯磺酰氧基四氢吡咯(1)为起始原料与二苯基膦化钠反应,再经膦硫化得到(2S,4S)-N-Boc-2-二苯硫膦甲基-4-二苯硫膦基四氢吡咯(2),收率67.2%;化合物2用过量的三氟乙酸处理脱去Boc保护基得到(2S,4S)-2-二苯硫膦甲基-4-二苯硫膦基四氢吡咯(3),收率94.0%;化合物3与N-Boc-L-天冬氨酸-4-苄酯缩合得到(2S,4S)-N-[(2′S)-2′-叔丁氧酰胺基-3′-苄氧酰基丙酰基]-2-二苯硫膦甲基-4-二苯硫膦基四氢吡咯(4),收率95.8%;化合物4再用三溴化硼脱去保护基得到目标产物(2S,4S)-N-[(2′S)-2′-氨基-3′-羧基丙酰基]-2-二苯硫膦甲基-4-二苯硫膦基四氢吡咯(5),收率54.2%。

Synthesis of a precursor compound of zwitterionic water-soluble chiral diphosphines ligands with amino acid moieties based on chiral diphosphines ligand PPM

The zwitterionic water-soluble chiral diphosphines ligands with amino acid moieties are synthesized based on chiral diphosphines ligand PPM.The reaction of(2S,4S)-N-Boc-4-(p-toluenesulfonyloxy)-2-[(p-toluenesulfonyloxy) methyl] pyrrolidine(1) with sodium diphenylphosphine and further treatments with sulfide can give in 67.2% yield the(2S,4S)-N-Boc-4-(diphenylphosphinothioyl)-2-[(diphenylphosphinothioyl) methyl] pyrrolidine(2),which is then converted by treatments with a excess of trifluoroacetic acid to(2S,...