Negishi applications

Negishi E, Novak T (2007) In Ojima I (ed) Applications II transition metal com-punds in organic synthesis 1. Comprehensive organometallic chemistry III, vol 10. Elsevier, Oxford, p 251... 

In conclusion, the fantastically diverse chemistry of indole has been significantly enriched by palladium-catalyzed reactions. The accessibility of all of the possible halogenated indoles and several indolyl triflates has resulted in a wealth of synthetic applications as witnessed by the length of this chapter. In addition to the standard Pd-catalyzed reactions such as Negishi, Suzuki, Heck, Stille and Sonogashira, which have had great success in indole chemistry, oxidative coupling and cyclization are powerful routes to a variety of carbazoles, carbolines, indolocarbazoles, and other fused indoles. 

The first highly stereoselective and satisfactory syntheses of conjugated dienes of general applicability are those based on organoboron chemistry reported by Negishi for (E,E) dienes and (E,Z) dienes as well as by Zweifel for (Z,Z) dienes. ... 

Negishi, K. and Ri, H. U. (1987). Propagation of multi-mode ultrasonic pulses in non-destructive material evaluation. In Ultrasonic spectroscopy and its application to materials Science (Ed. Y. Wada), pp. 70-4. Ministry of Education, Science, and Culture, Japan. [100,102]... 

Further applications of Negishi s cross-coupling reactions for the synthesis of new chiral ferrocenyl Ugands have been reported. Interestingly, cross-coupUng reactions can also be performed using triorganozincates, such as 454. Chloroenyne 455 reacts with various... 

The palladium catalyzed cross-coupling of organosilicon compounds and aryl halides found only limited application with azines compared to the Suzuki or Negishi coupling. In a recent paper DeShong reported the efficient coupling of bromopyridine derivatives with aryl siloxanes (7.44.) 62 The transmetalating ability of the siloxane was enhanced by the addition of tetrabutylammonium fluoride. 

Review. Negishi and Takahashi1 have reviewed the preparation and synthetic uses of organozirconium compounds, mainly of the type RZrCp2X. Because of the high cost of Zr compounds, most stoichiometric applications allow for recovery of the metallic compounds. The review covers more than 100 research papers, all published since 1970. 

The Negishi reaction was also found to be applicable to large-scale micro-wave-heated reactions. A previously published small-scale reaction (1 mmol) was easily transferred to a larger scale (2 x 20 mmol) and made to go to completion after only 1 minute of hold time with a very good isolated yield [90]. 

Negishi, E. in New Applications of Organometallic Reagents in Organic Synthesis (ed. Sey-feith, D.), p. 93, Elsevier, Amsterdam, 1976... 

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