Asymmetric C-C Bond Formation between Chiral N-Phosphonyl Imines and Ni(II)-Complex of Glycine Schiff Base Provides a GAP Synthesis of α,β-syn-Diamino Acid Derivatives.
Asymmetric C-C Bond Formation between Chiral N-Phosphonyl Imines and Ni(II)-Complex of Glycine Schiff Base Provides a GAP Synthesis of α,β-syn-Diamino Acid Derivatives.
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手性 N-膦酰亚胺和甘氨酸席夫碱 Ni(II) 复合物之间形成不对称 C-C 键，提供 α,β-syn-二氨基酸衍生物的 GAP 合成。
DOI：
10.1002/ejoc.201300554
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发表时间：
2013
影响因子：
2.8
通讯作者：
Li,Guigen
中科院分区：
文献类型：
--
作者：
Sun,Hao;Zhang,Haowei;Han,Jianlin;Pan,Yi;Li,Guigen
用NiII络合甘氨酸烯醇酯处理手性N-膦酰亚胺，实现了α，β-二氨基酸衍生物的基团辅助纯化不对称合成，不需要传统的层析、重结晶等纯化技术。邻二氨基产物的合成立体化学的成功控制是对我们以前提供抗立体异构体的方法的补充；因此，只需改变烯醇的几何构型就可以合成所有四个单独的异构体。与我们之前的合成相反，在合成中至少有5个当量。甘氨酸席夫碱烯醇酸需要完全转化，新的合成只需要1.1当量。甘氨酸席夫碱烯醇化可提供完全的非对映选择性(>；30：1DR)和高产率(91-97 %)。通过X射线结构分析明确确定了其绝对立体化学结构。
The group‐assisted purification asymmetric synthesis of α,β‐diamino acid derivatives was achieved by treating chiralN‐phosphonyl imines with a NiII‐complexed glycine‐derived enolate; traditional purification techniques such as chromatography and recrystallization are not required. Successful control of thesynstereochemistry of the vicinal diamino products complements our previous methods that affordedantistereoisomers; thus, all four individual isomers can be synthesized simply by changing the geometry of the enolate. In contrast to our previous synthesis in which at least 5 equiv. of the glycine Schiff base enolate was required for complete conversion, the new synthesis only needs 1.1 equiv. of the glycine Schiff base enolate to give complete diastereoselectivity (>30:1dr) and high yields (91–97 %). The absolute stereochemistry was unambiguously determined by X‐ray structure analysis.