- 著者
- Kazuhiko Semba Yoshiaki Nakao
- 出版者
- The Society of Synthetic Organic Chemistry, Japan
- 雑誌
- Journal of Synthetic Organic Chemistry, Japan (ISSN:00379980)
- 巻号頁・発行日
- vol.75, no.11, pp.1133-1140, 2017-11-01 (Released:2017-11-09)
- 参考文献数
- 154
- 被引用文献数
- 4
Cross-coupling reactions based on catalytically generated organocopper species have been developed by cooperative Pd/Cu or Ni/Cu catalysis. Alkyl or alkenylcopper intermediates generated via the hydrocupration or borylcupration of alkenes or alkynes engage in Pd- or Ni-catalyzed reactions with organic electrophiles. These reactions circumvent the laborious pre-synthesis and isolation processes of organometallics that characterize conventional cross-coupling reactions, and they are hence more step-economical. Moreover, highly functionalized organocopper species, which are difficult to access using conventional methods, can be obtained from readily available alkenes and alkynes. Thus, cross-coupling reactions by cooperative Pd/Cu or Ni/Cu catalysis represent powerful tools for the construction of complex structures from readily available starting materials in a single operation.
- 著者
- Yoshiaki Nakao
- 出版者
- (社)日本化学会
- 雑誌
- Bulletin of the Chemical Society of Japan (ISSN:00092673)
- 巻号頁・発行日
- pp.20120081, (Released:2012-06-28)
- 参考文献数
- 166
- 被引用文献数
- 72
Addition reactions of the organic and cyano groups of nitriles through cleavage of the C–CN bonds, namely carbocyanation, have been developed using nickel/Lewis acid (LA) cooperative catalysis. Originally, the reaction was performed with a nickel catalyst alone and was limited to the use of aryl and allyl cyanides as the nitrile substrates. By employing LA cocatalysts, the rate of the arylcyanation was accelerated significantly and the scope of nitriles used in the reaction across alkynes was expanded to include alkenyl, alkynyl, and alkyl cyanides. The high chemo-, regio-, and stereoselectivities of the alkyne–carbocyanation reactions were highlighted by the syntheses of biologically active compounds including the synthetic precursor of P-3622 and plaunotol, which possess defined tri- or tetrasubstituted ethene structures. Intramolecular arylcyanation of alkenes was also achieved by cooperative catalysis. Mechanistic studies on this particular transformation allowed us to identify several reaction intermediates, which revealed the modes of the cooperative catalysis derived from nickel- and aluminum-based LA. Intramolecular arylcyanation was achieved in an enantioselective manner using optically active bidentate phosphorus ligands, affording a protocol to introduce both a quaternary stereocenter and a cyano functionality without by-product generation.