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

• 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
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650918/
• 关键词: Ruthenium catalyst; Carbonylation; Dimerization; C-C bond cleavage; C-C bond formation; Cyclopropenone; Pyranopyrandione; Alkyne; 炭素-炭素結合切断; 炭素-炭素結合生成; ピロノピロン; アセチレン

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键的催化裂解一直是有机化学和有机金属化学领域最困难的挑战之一。这种化学最近受到了许多科学和技术的关注，并为合成有机化学的一个新领域打开了大门。下一个具有挑战性的课题是在C-C键断裂后重建新的碳骨架，从而快速和选择性地合成新的有机分子，这是传统合成方法的简单组合所无法获得的。在我们最近报道的钌催化的C-C键裂解反应中，首次进行了β-碳消除作用下叔烯丙醇选择性脱烯化反应机理的理论研究。然后，我们重点研究了环丙烯酮和环丁烯酮的反应性，它们是适合C-C键断裂的应变有机分子。经过多次试验，我们开发了一种前所未有的钌催化环丙烯羰基二聚化反应，涉及C-C键的裂解，从而得到了一种新的有机功能单体，pyranopyrandiones，收率高。此外，环普罗酮与炔的交叉羰基化反应也可以得到不对称取代的吡喃吡啶酮。另一方面，钌催化环丁烯酮二聚化合成2-吡喃酮的新方法也得到了发展。该反应可能通过一个η - 4-乙烯烯中间体进行，也有一些铑配合物催化反应，但在富Z钌和富E铑催化剂下的反应中，外烯基取代基的立体化学完全不同。

项目成果

Teruyuki Kondo: "Advances in Ruthenium Catalysis. Novel Catalytic Reactions via n^3-Allylruthenium Intermediates"Current Organic Chemistry. 6号. 1163-1179 (2002)

Teruyuki Kondo：“钌催化的进展。通过 n^3-烯丙基钌中间体的新型催化反应”《当前有机化学》第 6 期。1163-1179 (2002)

Teruyuki Kondo: "Advances in Ruthenium Catalysis Novel Catalytic Reactions via η^3-Allylruthenium Intermediates"Current Organic Chemistry. 6号. 1163-1179 (2002)

Teruyuki Kondo：“通过 η^3-烯丙基钌中间体实现钌催化新型催化反应的进展”《当前有机化学》第 6 期。1163-1179 (2002)

近藤 輝幸: "ルテニウム錯体触媒の特異的機能を活かした新規有機合成反応"有機合成化学協会誌. 59・3. 170-184 (2001)

Teruyuki Kondo：“利用钌配合物催化剂的特定功能的新有机合成反应”有机合成化学学会杂志 59・3（2001）。

Teruyuki Kondo: "Novel Synthesis of Benzenepolycarboxylates by Ruthenium-Catalyzed Cross-Benzannulation of Acetylenedicarboxylates with Allylic Compounds"Organometallics. 21・21. 4564-4567 (2002)

Teruyuki Kondo：“钌催化乙炔二羧酸酯与烯丙基化合物的苯多羧酸酯的新合成”有机金属学 21・21（2002）。

Take-aki Mitsudo: "Ruthenium Complex-Catalyzed Formation and Cleavage of Carbon-Carbon σ-Bonds. On the Requirement of Highly Qualified Tuning of the Reaction Conditions"Synlett. 3号. 309-321 (2001)

Take-aki Mitsudo：“钌配合物催化的碳-碳 σ-键的形成和裂解。关于反应条件的高质量调整的要求”Synlett No. 3. 309-321 (2001)。