The addition of organometallic reagents to carbonyl compounds has become a versatile method for synthesizing tertiary and secondary alcohols via carbon−carbon bond formation. However, due to the lack of good nucleophilicity or the presence of strong basicity of organometallic reagents, the efficientsynthesis of tertiary alcohols from ketones has been particularly difficult and, thus, limited. We recently
向羰基化合物中添加有机金属试剂已成为通过碳-碳键形成合成叔醇和仲醇的通用方法。然而,由于缺乏良好的亲核性或存在有机金属试剂的强碱性,由酮有效地合成叔醇特别困难并且因此受到限制。我们最近使用ZnCl 2,Me 3 SiCH 2开发了格氏试剂(RMgX:R =烷基,芳基; X = Cl,Br,I),对酮进行了高效的催化烷基化和芳基化反应MgCl和LiCl,可有效减少有问题的副反应。原则上,对于加成羰基化合物,RMgBr和RMgI的反应性不如RMgCl。因此,这种新颖的方法与均相催化的ZnCl 2 ·我3 SICH 2 MgCl·LiCl是相当有吸引力的,因为RMgBr和RMGI,其易于制备和/或可商购的,如RMgCl,可以成功地应用。除酮和醛以外,醛亚胺也有效地用于该催化反应,并以高收率获得了相应的仲胺。关于β-甲硅烷基效应和盐效应的机理细节,原位制备[R(Me 3 SiCH 2)2 Zn] -
Chemoselectivity of Nitroxylation of Cage Hydrocarbons
作者:Yu. N. Klimochkin、M. V. Leonova、E. A. Ivleva
DOI:10.1134/s107042802010005x
日期:2020.10
mixtures with acetic acid, aceticanhydride, and methylene chloride has been studied. More reactive substrates react with lowest selectivity regardless of the reaction medium. The primary nitroxylation products of cage hydrocarbons are nitrooxy derivatives. The compositions of reaction mixtures obtained in the reactions of some cage hydrocarbons with nitric anhydride in carbon tetrachloride have been determined
Processes for preparation of 2-alkyl-2adamantyl esters
申请人:——
公开号:US20030158437A1
公开(公告)日:2003-08-21
A magnesium halide salt of a 2-alkyl-2-adamantanol is reacted with a carboxylic acid halide such as acrylic chloride or the like in the presence of a tertiary amine to produce a 2-alkyl-2-adamantyl ester (the first invention).
A 2-alkyl-2-adamantanol is reacted with a carboxylic acid such as acrylic acid or the like in the presence of an acid catalyst such as concentrated sulfuric acid or the like and a drying agent composed of an acidic or neutral inorganic compound (e.g. magnesium sulfate) which is a solid at ordinary temperature in a dried state or of a water-absorbing high-molecular compound, to produce a 2-alkyl-2-admantyl ester (the second invention).
The above ester is important as a raw material for a resist for semiconductor production.