β-内酯的合成：一种用于环氧化合物羰基化反应的高活性和高选择性催化剂。

Synthesis of beta-lactones: a highly active and selective catalyst for epoxide carbonylation.

作者信息

Getzler Yutan D Y L, Mahadevan Viswanath, Lobkovsky Emil B, Coates Geoffrey W

机构信息

Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, USA.

出版信息

J Am Chem Soc. 2002 Feb 20;124(7):1174-5. doi: 10.1021/ja017434u.

DOI:10.1021/ja017434u

PMID:11841278

Abstract

A new highly active and selective catalyst for the synthesis of beta-lactones from CO and epoxides is reported. The catalyst, [(N,N'-bis(3,5-di-tert-butylsalicylidene) phenylenediamino)Al(THF)2][Co(CO)4] ([(salph)Al(THF)2][Co(CO)4]) is easily prepared from the corresponding (salph)AlCl and NaCo(CO)4. At 50 degrees C and 880 psi of CO, the catalyst (1 mol %) carbonylates epoxides such as propylene oxide, 1-butene oxide, epichlorohydrin, and isobutylene oxide to the lactones beta-butyrolactone, beta-valerolactone, gamma-chloro-beta-butyrolactone, and beta-methyl-beta-butyrolactone in high yield. (R)-Propylene oxide was carbonylated to (R)-beta-butyrolactone with retention of stereochemistry.

摘要

报道了一种用于由一氧化碳和环氧化物合成β-内酯的新型高活性和高选择性催化剂。该催化剂[(N,N'-双(3,5-二叔丁基水杨醛叉)苯二胺基)铝(四氢呋喃)₂]钴(羰基)₄可由相应的(salph)AlCl和NaCo(CO)₄轻松制备。在50℃和880 psi的一氧化碳条件下，该催化剂（1 mol%）可将环氧丙烷、1-丁烯氧化物、环氧氯丙烷和异丁烯氧化物等环氧化物高效羰基化为内酯β-丁内酯、β-戊内酯、γ-氯-β-丁内酯和β-甲基-β-丁内酯。(R)-环氧丙烷被羰基化为(R)-β-丁内酯，立体化学得以保留。