Asymmetric Construction of 3,4-Diamino Pyrrolidines via Chiral N,O-Ligand/Cu(I) Catalyzed 1,3-Dipolar Cycloaddition of Azomethine Ylides with β-Phthalimidonitroethene
Asymmetric Construction of 3,4-Diamino Pyrrolidines via Chiral N,O-Ligand/Cu(I) Catalyzed 1,3-Dipolar Cycloaddition of Azomethine Ylides with β-Phthalimidonitroethene
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DOI：
10.1021/acs.orglett.5b02431
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发表时间：
2015-10-16
期刊：
影响因子：
5.2
通讯作者：
Deng, Wei-Ping
中科院分区：
文献类型：
--
作者：
He, Fu-Sheng;Zhu, Han;Deng, Wei-Ping
研究了一系列1，2-二氢咪唑并[1，2-a]喹诺酮衍生的手性N，O-配体与偶极试剂β-邻苯二甲酰亚氨基硝基乙烯的偶氮甲碱叶立德的不对称1，3-偶极环加成反应。一个新设计的DHIPOH配体7 c带有1-甲基和4-碘代取代基，具有显著的“协同空间效应”，从而得到了相应的4-硝基-3-氨基吡咯烷，具有优良的非对映选择性（dr高达98：2）和对映选择性（ee高达99%）。随后的Raney Ni催化的邻苯二甲酰的还原和脱保护导致在结构和生物学上重要的3，4-二氨基吡咯烷在一个简单和有效的途径。
A series of chiral N,O-ligands derived from a 1,2-dihydroimidazo[1,2-a]quinolone motif have been evaluated for the asymmetric 1,3-dipolar cydoaddition of azomethine ylides with a novel dipolarophile beta-phthalimidonitroethene. A newly designed DHIPOH ligand 7c bearing 1-methyl and 4-iodo substituents was found to have significant "synergistic steric effects" and consequently afforded the corresponding 4-nitro-3-aminopyrrolidines with excellent diastereo- (dr up to 98:2) and enantio selectivities (ee up to 99%). Subsequent Raney Ni-catalyzed reduction and deprotection of phthalyl led to the structurally and biologically important 3,4-diaminopyrrolidines in a straightforward and efficient pathway.