N-Phosphinyl Imine Chemistry (I): Design and Synthesis of Novel N-Phosphinyl Imines and their Application to Asymmetric aza-Henry Reaction
N-Phosphinyl Imine Chemistry (I): Design and Synthesis of Novel N-Phosphinyl Imines and their Application to Asymmetric aza-Henry Reaction
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DOI：
10.1111/j.1747-0285.2010.01047.x
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发表时间：
2011-01-01
影响因子：
3
通讯作者：
Li, Guigen
中科院分区：
文献类型：
--
作者：
Pindi, Suresh;Kaur, Parminder;Li, Guigen
设计、合成了新型手性N-膦酰胺和N-膦酰亚胺，并将其应用于不对称氮杂-Henry反应，得到了良好的化学产率（92%- quant.）和非对映选择性（91%至> 99%de）。该反应显示了很大的底物范围，其中芳香族/脂肪族醛和酮衍生的N-膦基亚胺可以用作亲电试剂。手性N-膦酰胺可以在室温下储存超过2个月，而不需要惰性气体保护，手性N-膦基亚胺也被证明在室温下在惰性气体保护下长期高度稳定。N-氧膦基使得产物纯化能够简单地通过用EtOAc和己烷洗涤粗产物来进行。该反应加入了我们实验室开发的其他八个GAP（基团辅助纯化）化学过程。绝对构型已通过将β-亚硝胺产物转化为已知的N-Boc样品而明确确定。
Novel chiral N-phosphinamide and N-phosphinyl imines have been designed, synthesized and applied to asymmetric aza-Henry reaction to give excellent chemical yields (92%- quant.) and diastereoselectivity (91% to > 99%de). The reaction showed a great substrate scope in which aromatic/aliphatic aldehyde- and ketone-derived N-phosphinyl imines can be employed as electrophiles. The chiral N-phosphinamide can be stored at room temperature for more than 2 months without inert gas protection, and chiral N-phosphinyl imines were also proven to be highly stable at room temperature for a long period under inert gas protection. The N-phosphinyl group enabled the product purification to be performed simply by washing crude product with EtOAc and hexane. This reaction joined other eight GAP (Group-Assistant-Purification) chemistry processes that were developed in our laboratories. The absolute configuration has been unambiguously determined by converting a beta-nitroamine product into a known N-Boc sample.