用于合成官能化重氮乙酰乙酸酯的催化加成方法及其在构建高取代环丁酮中的应用。

Catalytic addition methods for the synthesis of functionalized diazoacetoacetates and application to the construction of highly substituted cyclobutanones.

作者信息

Doyle Michael P, Kundu Kousik, Russell Albert E

机构信息

Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USA.

出版信息

Org Lett. 2005 Nov 10;7(23):5171-4. doi: 10.1021/ol052003s.

DOI:10.1021/ol052003s

PMID:16268530

Abstract

[reaction: see text] Methyl 3-(trialkylsilanyloxy)-2-diazo-3-butenoate undergoes Lewis acid-catalyzed Mukaiyama aldol addition with aromatic and aliphatic aldehydes in the presence of low catalytic amounts of Lewis acids in nearly quantitative yields. Scandium(III) triflate is the preferred catalyst and, notably, addition proceeds without decomposition of the diazo moiety. Diazoacetoacetate products from reactions with aromatic aldehydes undergo rhodium(II)-catalyzed ring closure to cyclobutanones with high diastereocontrol. Examples of complimentary Mannich-type addition reactions with imines are reported.

摘要

[反应：见正文] 3-(三烷基硅烷氧基)-2-重氮-3-丁烯酸甲酯在低催化量的路易斯酸存在下，与芳香族和脂肪族醛发生路易斯酸催化的 Mukaiyama 羟醛加成反应，产率接近定量。三氟甲磺酸钪是首选催化剂，值得注意的是，加成反应进行时重氮部分不会分解。与芳香醛反应生成的重氮乙酰乙酸酯产物在铑(II)催化下进行闭环反应生成环丁酮，具有高非对映选择性。还报道了与亚胺的互补曼尼希型加成反应的实例。