β-内酯催化羰基化合成琥珀酸酐

Catalytic carbonylation of beta-lactones to succinic anhydrides.

作者信息

Getzler Yutan D Y L, Kundnani Vinod, Lobkovsky Emil B, Coates Geoffrey W

机构信息

Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853-1301, USA.

出版信息

J Am Chem Soc. 2004 Jun 9;126(22):6842-3. doi: 10.1021/ja048946m.

DOI:10.1021/ja048946m

PMID:15174834

Abstract

A well-defined, highly active and selective catalyst for the synthesis of succinic anhydrides from CO and beta-lactones is reported. At 200 psi of CO, the catalyst [(N,N'-bis(3,5-di-tert-butylsalicylidene)phenylenediamino)Al(THF)2][Co(CO)4] carbonylates beta-propiolactones to succinic anhydrides in high yield. (R)-beta-Butyrolactone is carbonylated to (S)-methylsuccinic anhydride with clean inversion of stereochemistry, while cis-2,3-dimethyl-beta-propiolactone yields exclusively trans-2,3-dimethylsuccinic anhydride. These data are consistent with a mechanism involving nucleophilic attack by [Co(CO)4]- on the beta carbon of the lactone, followed by CO insertion and anhydride formation.

摘要

报道了一种用于由一氧化碳和β-内酯合成琥珀酸酐的定义明确、活性高且选择性好的催化剂。在200磅力/平方英寸的一氧化碳压力下，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][Co(CO)₄]能将β-丙内酯高效地羰基化生成琥珀酸酐。(R)-β-丁内酯被羰基化为(S)-甲基琥珀酸酐，立体化学发生完全反转，而顺式-2,3-二甲基-β-丙内酯仅生成反式-2,3-二甲基琥珀酸酐。这些数据与一种机理相符，该机理涉及[Co(CO)₄]⁻对内酯β-碳的亲核进攻，随后是一氧化碳插入和酸酐形成。