Novel Catalytic Performance of Ruthenium Catalysts Toward the Characteristic Carbonylation Reactions

钌催化剂对特征羰基化反应的新型催化性能

基本信息

批准号：
11650872
负责人：
KONDO Teruyuki
金额：
$ 2.3万
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：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

项目摘要

A novel ruthenium catalyst system of[PPN][Ru_3H(CO)_<11>]/PCy_3[PPN=bis(triphenylphosphine)-iminium, Cy=cyclohexyl]for the direct hydroamidation and hydroesterification of alkenes with formamides and alkyl formates has been developed. These addition reactions proceeded smoothly under an argon atmosphere, and carbon monoxide is not needed to suppress decarbonylation of formyl compounds or to maintain the catalytic activity.On the other hand, during our effort to extend the previously reported ruthenium-catalyzed intermolecular Pauson-Khand reaction of 1, 6-enynes, we have found novel(η^3-C_3H_5)RuBr(CO)_3/Et_3N-catalyzed carbonylative cyclization of allylic carbonates with alkenes to give the corresponding cyclopentenones in high yields. In addition, cyclopentenones were prepared by a novel rutheniumcatalyzed coupling of cyclobutenediones with alkenes via C-C bond cleavage. For example, treatment of 4-butyl-3-isopropoxycyclobut-3-ene-1, 2-dione with 2-norbornene in the presence of a catalytic amount of Ru_3(CO)_<12> and PEt_3 in THF under 3 atm of carbon monoxide at 160℃ for 20 h gave the corresponding cyclopentenone, 4-butyl-5-isopropoxytricyclo[5.2.1.0^<2,6>]dec-4-en-3-one, in 75% yield(exo 100%). The reaction proceeds via a ruthenacyclopentenedione and/or ruthenacyclobutenone intermediate, which would be obtained by unsymmetrical ring-opening of cyclobutenediones with an active ruthenium catalyst.In coclusion, both reactions will open up new chemistry in the field of ruthenium-catalyzed carbonylation reactions, and offer the novel and practical methods for preparation of cyclopentenones which are quite attractive and important due to the wide abundance of this structural unit in a large number of natural products and biologically active compounds. These cyclopentenone syntheses may be the complement of the catalytic intermolecular Pauson-Khand reaction.

[PPN] [RU_3H（CO）_ <11>]/PCY_3 [PPN = BIS（Triphenyl磷酸）-Iminium，Cyclohexyl]的新型ruthenium催化剂系统，用于直接的氢化型和甲基烷基形式的烯烃。这些添加反应在氩气气下平稳地进行，不需要一氧化碳来抑制甲基化合物的脱轴词或维持催化活性。另一方面，在我们努力延长先前报道的氟他蛋白催化的分子间的pauson-khand反应1、6-元素反应的过程中，我们已经发现新颖的（η^3-C_3H_5）Rubr（CO）_3/ET_3N催化含有烯烃的Allic Carbonates的羰基环化环化，以高产量为相应的环戊烯酮。此外，通过C-C键裂解，通过新型的环丁酮与烯烃与烷烃的偶联耦合制备环戊烯酮。例如，在存在催化量的RU_3（CO）_ <12>的情况下，将4-叔丁基-3-异丙氧基三烯-3-ENE-1、2-二酮与2-雌激进烯进行处理。 4-叔丁基-5-异丙氧基曲与dec-4-en-3-One，收益率为75％（EXO 100％）。 The reaction proceeds via a ruthenacyclopentenedione and/or ruthenacyclobutenone intermediate, which would be obtained by unsymmetrical ring-opening of cyclobutenediones with an active ruthenium catalyst.In coclusion, both reactions will open up new chemistry in the field of ruthenium-catalyzed carbonylation reactions, and offer the novel and practical methods for preparation of由于在许多天然产物和生物学活性化合物中，该结构单元的广泛抽象，因此环戊烯酮非常有吸引力且重要。这些环烯酮合成可能是催化分子间Pauson-Khand反应的完成。