Pd-catalyzed allylic alkylation of secondary nitroalkanes
Pd-catalyzed allylic alkylation of secondary nitroalkanes
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DOI：
10.1016/j.tet.2007.03.062
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发表时间：
2007-05-14
期刊：
影响因子：
2.1
通讯作者：
Shibasaki, Masakatsu
中科院分区：
文献类型：
--
作者：
Maki, Keisuke;Kanai, Motomu;Shibasaki, Masakatsu
开发了一种钯催化仲硝基烷烃的烯丙基烷基化反应，使用催化量的外部碱。使用简单的碳酸烯丙酯和单取代的碳酸烯丙酯作为亲电子试剂，使用大体积的仲硝基烷烃作为亲核试剂。这是大体积仲硝基烷烃（例如 2-硝基庚烷）的首次催化烯丙基烷基化。在非质子极性溶剂DMSO中使用强碱DBU是实现高反应活性的关键。在开发不对称反应的尝试中，2-芳基恶唑啉配体PHOX L1在诱导π-烯丙基部分的手性方面给出了优异的结果。对于NO2官能团α位的不对称诱导，含有游离OH基团的2-芳基恶唑啉配体L4表现出中等选择性。 (C) 2007 Elsevier Ltd. 保留所有权利。
A Pd-catalyzed allylic alkylation of secondary nitroalkanes, using a catalytic amount of external base, was developed. Simple allyl carbonate and monosubstituted allyl carbonates were used as electrophiles, and bulky secondary nitroalkanes were used as nucleophiles. This is the first catalytic allylic alkylation of bulky secondary nitroalkanes, such as 2-nitroheptane. The use of the strong base DBU in the aprotic polar solvent DMSO is a key in realizing the high reactivity. In an attempt to develop an asymmetric reaction, 2-aryloxazoline ligand PHOX Ll gave excellent results for inducing chirality at the pi-allyl moiety. As for asymmetric induction at the a-position of the NO2 functionality, the free OH-group containing 2-aryloxazoline ligand L4 showed moderate selectivity. (C) 2007 Elsevier Ltd. All rights reserved.