165184-98-5Relevant articles and documents
Syngas-Free Highly Regioselective Rhodium-Catalyzed Transfer Hydroformylation of Alkynes to α,β-Unsaturated Aldehydes
Tan, Guangying,Wu, Yimin,Shi, Yang,You, Jingsong
, p. 7440 - 7444 (2019)
The hydroformylation of alkynes is a fundamental and important reaction in both academic research and industry. Conventional methods focus on the conversion of alkynes, CO, and H2 into α,β-unsaturated aldehydes, but they often suffer from problems associated with operation, regioselectivity, and chemoselectivity. Herein, we disclose an operationally simple, mild, and syngas-free rhodium-catalyzed reaction for the hydroformylation of alkynes via formyl and hydride transfer from an alkyl aldehyde. This synthetic method uses inexpensive and easy-to-handle n-butyraldehyde to overcome the challenge posed by the use of syngas in traditional approaches and employs a commercially available catalyst and ligand to transform a broad range of internal alkynes, especially alkynyl-containing complex molecules, into versatile stereodefined α,β-unsaturated aldehydes with excellent chemo-, regio-, and stereoselectivity.
Binuclear Pd(I)-Pd(I) Catalysis Assisted by Iodide Ligands for Selective Hydroformylation of Alkenes and Alkynes
Zhang, Yang,Torker, Sebastian,Sigrist, Michel,Bregovi?, Nikola,Dydio, Pawe?
supporting information, p. 18251 - 18265 (2020/11/02)
Since its discovery in 1938, hydroformylation has been thoroughly investigated and broadly applied in industry (>107 metric ton yearly). However, the ability to precisely control its regioselectivity with well-established Rh- or Co-catalysts has thus far proven elusive, thereby limiting access to many synthetically valuable aldehydes. Pd-catalysts represent an appealing alternative, yet their use remains sparse due to undesired side-processes. Here, we report a highly selective and exceptionally active catalyst system that is driven by a novel activation strategy and features a unique Pd(I)-Pd(I) mechanism, involving an iodide-assisted binuclear step to release the product. This method enables β-selective hydroformylation of a large range of alkenes and alkynes, including sensitive starting materials. Its utility is demonstrated in the synthesis of antiobesity drug Rimonabant and anti-HIV agent PNU-32945. In a broader context, the new mechanistic understanding enables the development of other carbonylation reactions of high importance to chemical industry.
Diphenylboron perchlorate as an efficient catalyst for self- and cross-condensation reactions of aldehydes having α-active hydrogens
Kiyooka, Syun-Ichi,Fujimoto, Hiroshi,Mishima, Masaaki,Kobayashi, Shinjiro,Uddin, Khabir Md.,Fujio, Mizue
, p. 927 - 930 (2007/10/03)
Diphenylboron perchlorate very smoothly catalyzed self- and cross-condensation reactions of aldehydes at rt in nitroethane. The new catalyst provided novel behaviors owing to the characteristics of possessing a covalency in the boron-oxygen bond, compared with ionic perchlorates.