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在未活化的伯碳和仲碳C-H键处进行的高对映选择性催化内酯化反应。

Highly Enantioselective Catalytic Lactonization at Nonactivated Primary and Secondary -C-H Bonds.

作者信息

Call Arnau, Capocasa Giorgio, Palone Andrea, Vicens Laia, Aparicio Eric, Choukairi Afailal Najoua, Siakavaras Nikos, López Saló Maria Eugènia, Bietti Massimo, Costas Miquel

机构信息

Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus Montilivi, Girona E-17071, Catalonia, Spain.

Dipartimento di Scienze e Tecnologie Chimiche, Università "Tor Vergata", Via della Ricerca Scientifica, 1 I-00133 Rome, Italy.

出版信息

J Am Chem Soc. 2023 Aug 16;145(32):18094-18103. doi: 10.1021/jacs.3c06231. Epub 2023 Aug 4.

Abstract

Chiral oxygenated aliphatic moieties are recurrent in biological and pharmaceutically relevant molecules and constitute one of the most versatile types of functionalities for further elaboration. Herein we report a protocol for straightforward and general access to chiral -lactones via enantioselective oxidation of strong nonactivated primary and secondary C()-H bonds in readily available carboxylic acids. The key enabling aspect is the use of robust sterically encumbered manganese catalysts that provide outstanding enantioselectivities (up to >99.9%) and yields (up to 96%) employing hydrogen peroxide as the oxidant. The resulting -lactones are of immediate interest for the preparation of natural products and recyclable polymeric materials.

摘要

手性氧化脂肪族部分在生物和药学相关分子中经常出现,并且是可进一步修饰的最通用的官能团类型之一。在此,我们报道了一种通过对易得羧酸中强的未活化伯、仲C()-H键进行对映选择性氧化直接且通用地获得手性内酯的方法。关键的促成因素是使用了空间位阻大的稳健锰催化剂,该催化剂使用过氧化氢作为氧化剂时可提供出色的对映选择性(高达>99.9%)和产率(高达96%)。所得内酯对于天然产物和可回收聚合物材料的制备具有直接的意义。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/abb9/10507665/8c43c5fb6647/ja3c06231_0001.jpg

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