通往季碳α-乙烯基氨基酸的一种形式上的[3,3] - 迁移重排途径：烯丙基N - PMP三氟乙酰亚胺酯的应用。
A formal [3,3]-sigmatropic rearrangement route to quaternary alpha-vinyl amino acids: use of allylic N-PMP trifluoroacetimidates.
作者信息
Berkowitz David B, Wu Bin, Li Huijie
机构信息
Department of Chemistry, University of Nebraska, Lincoln, Nebraska 68588-0304, USA.
出版信息
Org Lett. 2006 Mar 2;8(5):971-4. doi: 10.1021/ol060019s.
Abstract
Pd(II)-mediated rearrangement of allylic N-PMP (p-methoxyphenyl) trifluoroacetimidates provides the first formal sigmatropic route to quaternary, alpha-vinylic amino acids, potential suicide substrates for PLP enzymes. The amino acid side chains enter via transition-metal-mediated C-C bond constructions, including (i) Cu(I)-mediated conjugate addition (Ala); (ii) Pd(0)/AsPh3-mediated Stille coupling (allyl-Gly, Phe, DOPA, m-Tyr); and (iii) Pd(0)/Pt-Bu3-mediated Negishi coupling (Leu). In the synthesis of the DOPA decarboxylase inactivator, alpha-vinyl-m-tyrosine, the new N-PMP trifluoroacetimidate rearranges much more efficiently than the corresponding trichloroacetimidate.
摘要
钯（II）介导的烯丙基N - PMP（对甲氧基苯基）三氟乙酰亚氨酸酯重排为季碳α-乙烯基氨基酸提供了第一条形式上的[3,3] - 迁移途径，这些氨基酸是磷酸吡哆醛（PLP）酶潜在的自杀底物。氨基酸侧链通过过渡金属介导的C - C键构建引入，包括：（i）铜（I）介导的共轭加成（丙氨酸）；（ii）钯（0）/三苯基砷介导的施蒂勒偶联（烯丙基 - 甘氨酸、苯丙氨酸、多巴、间酪氨酸）；以及（iii）钯（0）/三叔丁基膦介导的根岸偶联（亮氨酸）。在多巴脱羧酶失活剂α-乙烯基 - 间酪氨酸的合成中，新的N - PMP三氟乙酰亚氨酸酯的重排比相应的三氯乙酰亚氨酸酯更有效。
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