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对映选择性铁催化的 O-H 键插入反应。

Enantioselective iron-catalysed O-H bond insertions.

机构信息

State Key Laboratory and Institute of Elemento-organic Chemistry, Nankai University, Tianjin 300071, China.

出版信息

Nat Chem. 2010 Jul;2(7):546-51. doi: 10.1038/nchem.651. Epub 2010 May 9.

Abstract

The ready availability, low price and environmentally benign character of iron mean that it is an ideal alternative to precious metals in catalysis. Recent growth in the number of iron-catalysed reactions reported reflects an increasing demand for sustainable chemistry. Only a limited number of chiral iron catalysts have been reported and these have, in general, proven less enantioselective than other transition-metal catalysts, thus limiting their appeal. Here, we report that iron complexes of spiro-bisoxazoline ligands are highly efficient catalysts for asymmetric O-H bond insertion reactions. These complexes catalyse insertions into the O-H bond of a wide variety of alcohols and even water, with exceptional enantioselectivities under mild reaction conditions. The selectivities surpass those obtained with other transition-metal catalysts. This study should inspire and encourage the use of iron instead of traditional precious metals in the development of greener catalysts for catalytic asymmetric synthesis.

摘要

铁具有易得、廉价和环境友好的特点,因此在催化领域是贵金属的理想替代品。最近报道的铁催化反应数量的增加反映了人们对可持续化学的需求不断增长。尽管已经报道了少量手性铁催化剂,但与其他过渡金属催化剂相比,这些催化剂的对映选择性通常较低,因此限制了它们的吸引力。在这里,我们报告了螺双恶唑啉配体的铁配合物是高效的不对称 O-H 键插入反应催化剂。这些配合物能够催化各种醇甚至水的 O-H 键插入,在温和的反应条件下具有出色的对映选择性。其选择性超过了其他过渡金属催化剂的选择性。这项研究应该会激发并鼓励在开发用于催化不对称合成的更环保的催化剂时使用铁代替传统贵金属。

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