Fukuyama coupling reaction

Fig. (33). Introduction of 4-carboxybutyl chani of 1 through the Fukuyama coupling reaction.

Tabic 11. Introducrion of 4-Carboxyb tyl Chain Through Fukuyama Coupling Reaction. 

Zinc dust was previously activated by the addition of carcinogenic 1,2-dibromoethane [0.026 equiv relative to zinc dust (Zn)] followed by chlorotrimethylsilane (TMSCl) (0.018 equiv relative to Zn), which gave rise to serious issues of poor reproducibility and requirement of excess iodide 80 (2.5 equiv relative to 8). Because the Fukuyama coupling reaction has been reported not to proceed with dialkyl zinc (R2Zn), the Schlenk equilibrium of the zinc reagent should lie to the left to achieve... 

Fig. (34). Schlenk equilibrium of zinc reagents and the utility for the Fukuyama coupling reaction.

A novel and practical synthesis of ( + )-biotin via the Fukuyama-coupling reaction 03YZ43. 

The Fukuyama indole synthesis involving radical cyclization of 2-alkenylisocyanides was extended by the author to allow preparation of2,3-disubstituted derivatives <00S429>. In this process, radical cyclization of 2-isocyanocinnamate (119) yields the 2-stannylindole 120, which upon treatment with iodine is converted into the 2-iodoindole 121. These N-unprotected 2-iodoindoles can then undergo a variety of palladium-catalyzed coupling reactions such as reaction with terminal acetylenes, terminal olefins, carbonylation and Suzuki coupling with phenyl borate to furnish the corresponding 2,3-disubstituted indoles. 

Fukuyama, Y., Y. Kiriyama, and M. Kodama. 1993. Concise synthesis of belamcan-daquinones A and by palladium (0) catalyzed cross-coupling reaction of bromo-quinone with arylboronic acids. Tetrahedron Lett. 34 7637-7638. 

Liu, S., Fukuyama, T., Sato, M. and Ryu, I. (2004) [Bmim]NTf2, a low viscosity ionic liquid is a viable reaction medium for Pd-catalyzed cross-coupling reactions. Synlett, 1814-6. 

T. Fukuyama, M. Shinmen, S. Nishitani, M. Sato, 1. Ryu, A copper-free Sonogashira coupling reaction in ionic liquids and its application to a microflow system for efficient catalyst recycling, Org. Lett, 2002, 4, 1691-1694. 

Fukuyama, T., et al., A copper-free Sonogashira coupling reaction in ionic liquids and its application to a microflow... 

Among MCRs, the Ugi reaction is a powerful three- or four-component coupling reaction with isocyanide as one of the reactants to construct multiple bonds in complex molecules. Applications of Ugi reactions in total synthesis are rather rare. One of the most advanced examples is the use in the total synthesis of ecteinascidin 743 48 by Fukuyama and coworkers, as depicted in Scheme 6.5 [22]. 

Scheme 7.36 [RuHCKCOjtPPhjjjJ-catalyzed coupling reaction of arylboronic adds with aryl aldehydes, as described by Fukuyama and coworkers [54],...

Fukuyama, T., Shinmen, M., Nishitani, S., Sato, M. Ryu, I. (2002). A Copper-Free Sonogashira Coupling Reaction in Ionic Liquids and Its Application to a Microflow System for Efficient Catayst Recycling, Org. lett., 4, p>p. 1691-1694... 

Sugimoto A., Fukuyama T., Rahman M., Ryu I. An automated-flow microreactor system for quick optimization and productiomapplication of 10-and 100-gram order productions of a matrix metalloproteinase inhibitor using a Sonogashira coupling reaction. Tetrahedron Lett. 2009 50 (46) 6364-6367. 

Scheme 17.1 Bidirectional solid-phase total synthesis of AigTX-636. The monoprotected diamine was anchored to the resin by reduced amination, followed by adding the amino acid linker and aromatic head group under the standard coupling condition. The polyamine backbone was prolonged by repeated Fukuyama-Mitsunobu reactions. After adding the terminal arginine to the intermediate, the protected resin-bound molecule was released from the resin, and then the protecting group was removed to obtain the nature ArgTX-636...

Many pyridine-indole compounds are biologically active. A growing number of methods for the preparation of indolylstannanes have been developed. 2-Trialkylstannylindoles, for example, have been synthesized via directed metalation followed by reaction with tin chloride [91-93]. The latest indolylstannane syntheses include Fukuyama s free radical approach to 2-trialkylstannylindoles from novel isonitrile-alkenes [94], and its extension to an isonitrile-alkyne cascade [95]. Assisted by the chelating effect of the SEM group oxygen atom, direct metalation of 1-SEM-indole and transmetalation with BujSnCl afforded 2-(tributylstannyl)-l//-indole 108, which was then coupled with 2,6-dibromopyridine to give adduct 109. 

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