Kaithal Akash, Gracia Lisa-Lou, Camp Clément, Quadrelli Elsje Alessandra, Leitner Walter
Institut für Technische und Makromolekulare Chemie , RWTH Aachen University , Worringer Weg 2 , 52074 Aachen , Germany.
Laboratory of Chemistry, Catalysis, Polymers and Processes , C2P2 UMR 5265, Université de Lyon, Institut de Chimie de Lyon, CNRS, Université Lyon 1, ESCPE Lyon , 43 Bd du 11 Novembre 1918 , F-69616 Villeurbanne , France.
J Am Chem Soc. 2019 Nov 6;141(44):17487-17492. doi: 10.1021/jacs.9b08832. Epub 2019 Oct 29.
A method for the synthesis of substituted cycloalkanes was developed using diols and secondary alcohols or ketones via a cascade hydrogen borrowing sequence. A non-noble and air-stable manganese catalyst (2 mol %) was used to perform this transformation. Various substituted 1,5-pentanediols (3-4 equiv) and substituted secondary alcohols (1 equiv) were investigated to prepare a collection of substituted cyclohexanes in a diastereoselective fashion. Similarly, cyclopentane, cyclohexane, and cycloheptane rings were constructed from substituted 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol, and sterically hindered ketones following a (4 + 1), (5 + 1), and (6 + 1) strategy, respectively. This reaction provides an atom economic methodology to construct two C-C bonds at a single carbon center generating high-value cycloalkanes from readily available alcohols as feedstock using an earth-abundant metal catalyst.
通过级联氢转移序列，开发了一种使用二醇与仲醇或酮合成取代环烷烃的方法。使用一种非贵金属且空气稳定的锰催化剂（2 mol%）来进行这种转化。研究了各种取代的1,5-戊二醇（3 - 4当量）和取代的仲醇（1当量），以非对映选择性的方式制备一系列取代的环己烷。类似地，分别按照（4 + 1）、（5 + 1）和（6 + 1）策略，由取代的1,4-丁二醇、1,5-戊二醇和1,6-己二醇以及空间位阻酮构建环戊烷、环己烷和环庚烷环。该反应提供了一种原子经济的方法，在单个碳中心构建两个C - C键，使用储量丰富的金属催化剂，以易得的醇为原料生成高价值的环烷烃。
