4980-70-5Relevant articles and documents
Organoborane-catalyzed selective 1,2-reduction of alkynones with hydride transfer: Synthesis of benzyl alkynes
Zhai, Lele,Yang, Zhigang,Man, Qinghong,Yang, Mingyu,Ren, Yangqing,Wang, Lei,Li, Huilin,She, Xuegong
, (2022/01/28)
Benzyl alkynes are important organic building blocks in organic synthesis. We report herein a B(C6F5)3-catalyzed site-selective 1,2-reduction of readily available alkynones to access benzyl alkyne derivatives. Under the de
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.
Regioselective Iron-Catalysed Cross-Coupling Reaction of Aryl Propargylic Bromides and Aryl Grignard Reagents
Manjón-Mata, Inés,Quirós, M. Teresa,Bu?uel, Elena,Cárdenas, Diego J.
supporting information, p. 146 - 151 (2019/12/11)
An iron-catalysed Kumada-type cross-coupling reaction between aryl substituted propargylic bromides and arylmagnesium reagents has been developed. Propargylic coupling products were the main or only outcome, and propargyl/allene regioselectivity was shown to depend on the electronic nature of the substituents on the triple bond of the substrate and on the arylmagnesium halide. Best selectivities were observed when electron donating substituents were present in either reagent. The process is stereoespecific, occurs with configuration inversion and no carbon-based radicals seem to be involved in the mechanism. (Figure presented.).
