A new nickel-catalyzed synthesis of aromatic nitriles

Cassar, L.

doi:10.1016/s0022-328x(00)84982-7

Cited by 109 publications

(27 citation statements)

References 6 publications

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“…It was demonstrated in 1973 that [(PCy 3 ) 2 Ni(1-naphthyl)Cl] could be used as a precatalyst for the cyanation of aryl halides 144 . Despite this seminal work, there were relatively few additional reports describing the use of σ -aryl complexes as precatalysts for cross-coupling until the late 2000s.…”

Section: Ni-based Precatalystsmentioning

confidence: 99%

Well-defined nickel and palladium precatalysts for cross-coupling

2017

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Transition metal-catalysed cross-coupling is one of the most powerful synthetic methods and has led to vast improvements in the synthesis of pharmaceuticals, agrochemicals and precursors for materials chemistry. A major advance in cross-coupling over the past 20 years is the utilization of well-defined, bench-stable Pd and Ni precatalysts that do not require the addition of free ancillary ligand, which can hinder catalysis by occupying open coordination sites on the metal. The development of precatalysts has resulted in new reactions and expanded substrate scopes, enabling transformations under milder conditions and with lower catalyst loadings. This Review highlights recent advances in the development of Pd and Ni precatalysts for cross-coupling, and provides a critical comparison between the state of the art in Pd- and Ni-based systems.

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Section: Ni-based Precatalystsmentioning

confidence: 99%

Well-defined nickel and palladium precatalysts for cross-coupling

2017

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“…Photoirradiation was examined with a solution of C 6 D 6 containing [Cp(CO) 2 [25] (54 % yield by NMR spectroscopy), a signal at 0.15 ppm due to CH 4 Et 3 SiÀSiEt 3 would be formed if the two silyl groups were eliminated reductively from the species.…”

Section: )] As Well As Co Dissociation From [Cp(co) 2 Feme] the [Cp(mentioning

confidence: 99%

“…[2][3][4][5][6][7][8][9][10] Furthermore, one example each of Mo, [11] Co, [12] and U [13] and two examples of Cu [14,15] were reported. They mainly involve Group 10 transition-metal triads.…”

mentioning

confidence: 99%

Iron‐Complex‐Catalyzed CC Bond Cleavage of Organonitriles: Catalytic Metathesis Reaction between HSi and RCN Bonds to Afford RH and SiCN Bonds

Nakazawa

Itazaki

Kamata

et al. 2007

Chemistry An Asian Journal

106

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The first example of the catalytic C-CN bond cleavage of acetonitrile as well as Si-CN bond formation have been achieved in the photoreaction of MeCN with Et3SiH promoted by [Cp(CO)2FeMe]. This catalytic system is applicable to other organonitriles. Several iron complexes [(eta(5)-C5R5)(CO)2FeR'] (R5 = H5, H4Me, Me5, H4SiMe3, H4I, H4P(O)(OMe)2; R' = SiMe3, CH2Ph, Me, Cl, I) were examined as catalyst, and [Cp(CO)2FeMe] was found to be the best precursor. A catalytic reaction cycle was proposed, which involves oxidative addition of Et3SiH to [Cp(CO)FeMe], reductive elimination of CH4 from [Cp(CO)FeMe(H)(SiEt3)], coordination of RCN to [Cp(CO)Fe(SiEt3)], silyl migration from Fe to N in the coordinated RCN, and dissociation of Et3SiNC from Fe. The reaction with MeCN of [Cp(CO)Fe(py)(SiEt3)], which was newly prepared and determined by X-ray analysis, and the reaction of Et3SiH with MeCN in the presence of a catalytic amount of [Cp(CO)Fe(py)(SiEt3)] showed that the 16-electron species [Cp(CO)Fe(SiEt3)] is the active species in the catalytic cycle (TON up to 251).

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“…The subsequent reductive elimination of CH 4 yields CpFe(CO)(SiEt 3 ). As SiEt 3 Me was not observed at all in this system, reductive elimination of CH 4 Proposed catalytic cycle.…”

Section: Consideration Of Catalytic Cyclementioning

confidence: 84%

“…Transition metal complexes have been used to attain C-C bond cleavage of nitrile. They mainly involve Group 10 transition metal triads [2][3][4][5][6][7][8][9][10]. In addition, one example for Mo [11], Co [12], U [13], and two examples of Cu [14,15] have been reported.…”

Section: Introductionmentioning

confidence: 99%

Strong bond cleavage promoted by silyl group migration in a coordination sphere

Nakazawa

2011

WIT Transactions on Ecology and the Environment

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C-CN bond cleavage in organonitriles was attained in the photoreaction with HSiEt 3 in the presence of a catalytic amount of ( 5 -C 5 H 5 )Fe(CO) 2 Me. The reaction sequence was proposed, where silyl migration from Fe to N in the coordinating nitrile is a key step. DFT calculations proposed a silyl migration with small activation energy of 4.0 kcal/mol and subsequent C-CN bond cleavage on the Fe coordination sphere. N-CN bond cleavage in cyanamide (R 2 NCN) was also attained by a transition metal catalyst. A catalytic cycle was proposed where a silyl migration from a transition metal to the nitrile nitrogen is involved. An N-silylated  2 -amidino complex was isolated, which was shown to be an intermediate in the catalytic pathway.

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A new nickel-catalyzed synthesis of aromatic nitriles

Cited by 109 publications

References 6 publications

Well-defined nickel and palladium precatalysts for cross-coupling

Well-defined nickel and palladium precatalysts for cross-coupling

Iron‐Complex‐Catalyzed CC Bond Cleavage of Organonitriles: Catalytic Metathesis Reaction between HSi and RCN Bonds to Afford RH and SiCN Bonds

Strong bond cleavage promoted by silyl group migration in a coordination sphere

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