Novel Organic Syntheses by Reconstruction of Carbon Skeletons via Catalytic Carbon-Carbon Bond Cleavage

通过催化碳-碳键断裂重建碳骨架进行新型有机合成

基本信息

批准号：
13650918
负责人：
KONDO Teruyuki
金额：
$ 2.62万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2002
项目状态：
已结题

项目摘要

The catalytic cleavage of C-C bonds has been one of the most difficult challenges in the fields of organic and organometallic chemistry. This chemistry has recently received much scientific and technological interest, and has opened the door to a new field of synthetic organic chemistry. The next challenging subject is the reconstruction of new carbon skeletons after C-C bond cleavag, leading to the rapid and selective synthesis of novel organic molecules which can not be obtained by the simple combination of traditional synthetic methods. Among our recent reports on the ruthenium-catalyzed C-C bond cleaving reactions, the theoretical study for mechanism on the selective deallylation of tertiary homoallyl alcohols involving β-carbon elimi nation was first carried out. Then, we focused our attention on the reactivity of cyclopropenones and cyclobutenones which are the suitable strained organic molecules for C-C bond cleavage. After many trials, we developed an unprecedented ruthenium-catalvzed carbonylative dimerization of cyclopropenones involving C-C bond cleavage, which gave a novel organic functional monomer, pyranopyrandiones, in high yield. Furthermore, cross-carbonylation of cycloprorenones with alkynes was also found to give unsymmetrically substituted pyranopyrandiones. On the other hand, novel ruthenium-catalyzed dimerization of cyclobutenones to 2-pyranones has also been developed. This reaction may proceed via an η4-vinylketene intermediate, The reaction was also catalyzed by some rhodium complexes, however, the stereochemistry of the external alkenyl-substituent is totally different between the reactions using ruthenium (Z rich) and rhodium (E rich) catalysts.

C-C键的催化切割一直是有机和有机化学领域中最困难的挑战之一。该化学最近引起了很多科学和技术兴趣，并为新的合成有机化学领域打开了大门。下一个挑战主题是在C-C键链球化后重建新的碳骨架，从而导致新型有机分子的快速和选择性合成，这些合成无法通过传统合成方法的简单组合而获得。在我们最近关于芳族催化的C-C键切割反应的报道中，首先进行了有关涉及β-碳二烯丙基甲基甲基乙醇的第三级同甲醇的选择性交易的理论研究。然后，我们将注意力集中在环丙酮和环丁酮的反应性上，这些反应性是适合C-C键裂解的合适的有机分子。经过多次试验，我们开发了一种前所未有的芳族芳族 - catalvzed carbonyldimimerization，涉及C-C键裂解的环丙烯二聚二聚二聚体，该型具有很高的产量，从而给出了一种新型的有机功能性单体，吡喃吡丹酮。此外，还发现环丙烯酮用酒精酮的交叉键盘化给出了非对称取代的吡喃吡班二酮。另一方面，也已经开发了新型的氟苯丁烯蛋白化合物对2-吡喃酮的二聚化。该反应可以通过η4-乙烯基酮的中间体进行，一些仇恨复合物也催化了反应，但是，使用氟苯（Z Rich）和犀牛（E Rich）催化剂的反应之间的外部烷烯基 - 叠加物的立体化学完全不同。