Novel Catalytic Performance of Ruthenium Catalysts Toward the Characteristic Carbonylation Reactions

本文报道了[PPN][Ru_3H（CO）_<11>]/PCy_3[PPN=双（三苯基膦）亚胺，Cy=环己基]钌催化体系在烯烃与甲酰胺和甲酸酯的直接氢酰胺化和氢酯化反应中的应用。这些加成反应在氩气气氛下顺利进行，并且不需要一氧化碳来抑制甲酰基化合物的脱羰基反应或保持催化活性。另一方面，在我们努力扩展先前报道的1，6-烯炔的铼催化的分子间Pauson-Khand反应的过程中，我们发现了一种新的（η^3-C_3H_5）RuBr（CO）_3/Et_3 N催化烯丙基碳酸酯与烯烃的羰基环化反应，高产率地得到了相应的环戊烯酮。此外，还研究了一种新的环丁烯二酮与烯烃的C-C键裂解偶联反应，制备了环戊烯酮。例如，4-丁基-3-异丙氧基环丁-3-烯-1，2-二酮与2-异丙基烯在催化量的Ru_3（CO）_和PEt_3存在<12>下在THF中在3atm的一氧化碳下在160℃下反应20小时，得到相应的环戊烯酮，4-丁基-5-异丙氧基三环[5.2.1.0 ^&lt;2，6&gt;]癸-4-烯-3-酮，产率为75%（exo 100%）。该反应通过环丁烯二酮在活性钌催化剂作用下不对称开环得到的环己烯环戊烯二酮和/或环己烯环丁烯酮中间体进行，这两个反应将在钌催化的羰基化反应领域开辟新的化学，并提供了新的和实用的方法来制备环戊烯酮，这是非常有吸引力的和重要的，由于这一广泛的丰富，在大量的天然产物和生物活性化合物的结构单元。这些环戊烯酮的合成可能是催化分子间Pauson-Khand反应的补充。

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.