Syntheses of condensed pyrimidines as organic catalysts and the biomimetic redox catalyzed by them

有机催化剂稠合嘧啶的合成及其催化的仿生氧化还原

基本信息

批准号：
05680505
负责人：
NAGAMATSU Tomohisa
金额：
$ 1.28万
依托单位：
Okayama University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1993
资助国家：
日本
起止时间：
1993 至 1994
项目状态：
已结题

项目摘要

1) During the search for an efficient autorecycling oxidation catalyst, pyridodipyrimidine derivatives, new type NAD models, have been found to work under neutral conditions in oxidation of alcohols. This time, pyrimidopteridine derivatives as the catalysts, new type flavin models, were selected in the autorcycling oxidation. Actually, the pyrimidopteridines oxidized not only a variety of alcohols but also amines under neutral conditions at 120ﾟC for 10-25 hours to yield the corresponding carbonyl compounds and imines, catalytically with a markedly high turnover number (ca.20-180 turnover number).2) The biomimetic reduction of carbonyl compounds by NADH models such as N-alkylnicotinamides or Hantzsch esters has been extensively studied. However, these NADH models can reduce only carbonyl compounds which are highly activated by the presence of electron-deficient or by the presence of metal ions. In 1978, Yoneda et al.were reported first example of the reduction of inactivated simple carbonyl substrates to the corresponding alcohols by 1,5-dihydro-5-deazaflavin in the presence of strong proton sources such as hydrochloric acid or trifluoroacetic acid in stoichiometric yields. We studied now the autorecycling reduction of carbonyl compounds to alcohols by 1,5-dihydro-5-deazaflavins which are produced by 5-deazaflavin and formic acid in a circulatory system. In particular, the reduction using 3,7-dimethyl-10-p-tolyl-5-deazaflavin at 120ﾟC for 50 hours proceeded until the benzaldehyde substrate was exhausted to give 100% yield of benzyl alcohol. The yield based on the catalyst was 3129%, which means 31 recyclings of the catalyst. Morcover, a useful autorecycling system for the specific 1,4-reduction of alpha, beta-unsaturated carbonyl compounds to the corresponding saturated carbonyl compounds catalyzed by the 3,7-dimethyl-10-p-tolyl-5-deazaflavin in formic acid was studied.

1）在寻找自循环高效氧化催化剂的过程中，发现吡啶二嘧啶衍生物，新型NAD模型，在中性条件下可用于醇的氧化，本次选择嘧啶蝶啶衍生物作为催化剂，新型黄素模型。实际上，嘧啶蝶啶在中性条件下不仅可以氧化多种醇，还可以氧化胺。在120°C条件下反应10-25小时，产生相应的羰基化合物和亚胺，催化作用具有显着高的周转数（约20-180周转数）。2）NADH模型（例如N）对羰基化合物的仿生还原烷基烟酰胺或 Hantzsch 酯已被广泛研究，然而，这些 NADH 模型只能还原因缺电子的存在而高度活化的羰基化合物。 1978 年，Yoneda 等人报道了在强质子源（例如，1,5-二氢-5-脱氮黄素）存在下将失活的简单羰基底物还原为相应醇的第一个例子。我们现在研究了化学计量产率的盐酸或三氟乙酸将羰基化合物自动循环还原为醇。 1,5-二氢-5-去氮黄素是由5-去氮黄素和甲酸在循环系统中产生的，特别是使用3,7-二甲基-10-对甲苯基-5-去氮黄素在120℃下还原。进行50小时直至苯甲醛底物耗尽，得到100%收率的苯甲醇。基于催化剂的收率是。 3129%，这意味着催化剂的 31 次循环利用，Morcover 是一种有用的自动循环系统，用于在 3,7-二甲基-10-催化下将 α,4-不饱和羰基化合物还原为相应的饱和羰基化合物。研究了甲酸中的对甲苯基-5-脱氮黄素。