Arylcyanation of Norbornene and Norbornadiene Catalyzed by Nickel

Nakao, Yoshiaki; Yada, Akira; Satoh, Jun; Ebata, Shiro; Oda, Shinichi; Hiyama, Tamejiro

doi:10.1246/cl.2006.790

Cited by 73 publications

(39 citation statements)

References 16 publications

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“…On the other hand, ee the reaction of an aryl cyanide with triethoxy(vinyl)silane gives a Heck-type arylation product, suggesting the arylnickelation pathway in the catalytic cycle. 68 Nickel(0)-catalysed hydrocyanation of certain 1,3-dienes with 1,2-bisdiarylphosphinites as chiral ligands has been developed as an efficient method. Thus, 1-phenylbuta-1,3-diene, 1-vinyl-3,4-dihydronaphthalene, and 1-vinylindene undergo highly regioselective hydrocyanation under ambient conditions to give exclusively the 1,2-ee adducts in good to excellent yields.…”

Section: Additions Initiated By Metals and Metal Ions As Electrophilesmentioning

confidence: 99%

“…88 Palladium-monophosphine complexes catalyse trans-selective arylative, alkenylative, and alkylative cyclization reactions of alkynals [e.g. (68)] and alkynones with organoboronic reagents. These reactions afford six-membered allylic alcohols (69) de and/or their five-membered counterparts (70), whose ratios are dramatically affected …”

Section: Additions Initiated By Metals and Metal Ions As Electrophilesmentioning

confidence: 99%

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Addition Reactions: Polar Addition

Kočovský

2010

Organic Reaction Mechanisms · 2006

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Section: Additions Initiated By Metals and Metal Ions As Electrophilesmentioning

confidence: 99%

Section: Additions Initiated By Metals and Metal Ions As Electrophilesmentioning

confidence: 99%

Addition Reactions: Polar Addition

Kočovský

2010

Organic Reaction Mechanisms · 2006

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“…24 Subsequently, we reported the arylcyanation of bicyclic alkenes such as norbornene and norbornadiene (eq 7), 25 the allylcyanation of alkynes (eq 8), 26 and the cyanoesterification of 1,2-dienes (eq 9), 27 all catalyzed by nickel, demonstrating that nickel catalysis is highly versatile in the carbocyanation reactions of unsaturated compounds. Nevertheless, the scope of useful nitriles was difficult to further expand with the nickel catalyst alone, and the reaction conditions needed improvement in terms of catalyst loading and reaction temperature.…”

Section: Introductionmentioning

confidence: 99%

Nickel/Lewis Acid-Catalyzed Carbocyanation of Unsaturated Compounds

Nakao

2012

Bulletin of the Chemical Society of Japan

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Addition reactions of the organic and cyano groups of nitriles through cleavage of the CCN 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 alkynecarbocyanation 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.

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“…32 One isolated example of a Mizoroki Heck type alkenylation of nitriles (34% yield), in which a C CN bond is cleaved via oxidative addition to a nickel catalyst, has been reported. 33 The effect of the substituents on the silicon atom of the vinylsilanes was examined ( Table 8). The use of vinylsilanes bearing trimethyl , t butyldimethyl , and triisopropylsilyl groups, as in 26b d, lowered the yields of the corresponding alkenylated products.…”

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confidence: 99%

Rhodium-Catalyzed Carbon-Cyano Bond Cleavage Reactions Using Organosilicon Reagents

Kita¹,

Tobisu

Chatani

2010

J. Synth. Org. Chem. Jpn.

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Rhodium catalyzed carbon cyano bond cleavage reactions using organosilicon reagents are described. When disilane is used as the silicon reagent, the C CN bonds in aryl and alkenyl cyanides are silylated to form the corresponding silylated products along with silyl cyanide. Reductive decyanation of nitriles is achieved when hydrosilane is used as the silicon reagent. In addition, this catalytic system can be applied to the C(sp 3 ) CN bonds in simple aliphatic nitriles. In both reactions, the silylrhodium species generated in situ serves as a catalytically active species, cleaving C CN bonds via an η 2 iminoacyl complex. Addition of external electrophiles allowed the silicon assisted cleavage of C CN bonds to be applied to C C bond formation reactions. Intramolecular arylation of benzonitrile bearing a tethered chlorophenyl group and decyanative Mizoroki Heck type alkenylation of nitriles with vinylsilanes have been developed.

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Arylcyanation of Norbornene and Norbornadiene Catalyzed by Nickel

Cited by 73 publications

References 16 publications

Addition Reactions: Polar Addition

Addition Reactions: Polar Addition

Nickel/Lewis Acid-Catalyzed Carbocyanation of Unsaturated Compounds

Rhodium-Catalyzed Carbon-Cyano Bond Cleavage Reactions Using Organosilicon Reagents

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