过渡金属多相催化分子氧选择性氧化邻二醇的研究进展

Advances in selectively aerobic oxidation of vicinal diols catalyzed by heterogeneous transition metal catalysts

邻二醇选择性氧化断键生成醛、酮和羧酸是重要和基本的有机反应,氧化剂通常采用化学计量的高碘酸盐或四乙酸铅,无论从经济还是环保的角度考虑,这些传统方法都有违绿色化工的发展理念。理论上以分子氧为氧化剂选择性氧化邻二醇断键的副产物只有水,而且分子氧廉价易得,因而具有环境友好和经济可行的双重优势。经过多年探索,人们已开发了多个基于不同过渡金属为活性组分的多相催化剂或催化体系用于分子氧选择性氧化邻二醇断键反应,为未来广泛应用奠定了基础。该文按贵金属和非贵金属分类综述此类催化剂及相关反应工艺的研究进展,并指出该领域的发展方向。

Selectively oxidative cleavage of vicinal diols to generate corresponding aldehydes,ketones and carboxylic acids is an important and basic organic reaction,in which stoichiometric periodate or lead tetraacetate are usually employed as oxidants.Obviously,these traditional protocols are contrary to the development concept of green chemical industry in views of both economic and environmental standards.In principle,water is the only by-product in the selective oxidation cleavage of vicinal diols when molecular oxygen,cheap and readily available,is used as oxidant,leading to the dual advantages of environmental friendliness and economic feasibility.Therefore,a number of heterogeneous catalysts or catalytic systems with different transition metals as active components have been developed for such reaction after unremitting exploration,which provides groundwork for widespread application in the future.Herein,the advances of these catalysts and reaction processes by classifications of precious and non-precious metals were summarized,and the development direction in this field was pointed out.