Ni(0)/NHC-catalyzed amination of N-heteroaryl methyl ethers through the cleavage of carbon‒oxygen bonds

Tobisu, Mamoru; Yasutome, Ayaka; Yamakawa, Ken; Shimasaki, Toshiaki; Chatani, Naoto

doi:10.1016/j.tet.2012.04.005

Cited by 91 publications

(56 citation statements)

References 42 publications

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“…After the development of improved conditions, ArOR can now be used as a coupling partner in several types of transition metal (TM)-catalyzed cross-couplings and related transformations, such as Suzuki-Miyaura-type (B), [24][25][26][27][28][29][30][31] Negishi-type (Zn or Al), [32][33][34][35][36] Murahashi-type (Li), [37][38][39][40] and other reactions. [41][42][43][44][45][46][47][48][49][50] As a continuation of our work in this area, we reported in 2012 the first ethereal Negishi-type coupling of aryl alkyl ether 36) (Chart 1(1)) and in 2016 we reported a systematic examination of ethereal Murahashi-type reaction 37) (Chart 1(2)). More recently, we also reported an in-depth study of Ni-catalyzed cross-coupling between organoaluminums and various types of C-O electrophiles, including aryl alkyl ether.…”

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confidence: 72%

Ethereal C–O Bond Cleavage Mediated by Ni(0)-Ate Complex: A DFT Study

et al. 2017

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Density functional theory calculations were performed to explore the mechanism of Ni-catalyzed crosscoupling reactions involving organo-lithium and -zinc reagents through ethereal C-O bond cleavage. Based on this work, together with our previous mechanistic study on etheric Kumada-Tamao reaction, we identify and characterize a novel catalytic cycle for cross-coupling mediated by Ni(0)-ate complex.Key words cross-coupling; ether; nickel catalyst; organolithium; organozinc; density functional theory (DFT) calculation Efficient and selective cleavage and transformation of C-O bonds, particularly by means of cross-coupling methods, has attracted great interest, since compounds containing C-O moieties occur widely in nature and are also extensively utilized in industry.1-8) Among C-O compounds, ethers are particularly attractive, [1][2][3][4][5][6][7][8] as they offer the advantages of 1) high atom economy/conversion efficiency (the use of ethers as simple as MeO as substrates affords fewer by-products compared with tosylate, mesylate, triflate, phosphate, etc.), 2) environmental compatibility (cleavage of the C-O moiety in ether releases non-halogen-containing waste), and 3) excellent stability, easy accessibility and wide diversity. However, ethereal C-O bonds ( E C-O) are very unreactive, and most of the well-established Pd-catalyzed C-O bond-cleaving protocols are ineffective for ethers.On the other hand, Ni-catalysts have proved effective for many types of C-O bond cleavage, including ethers. As early as in 1979, Wenkert et al. 9,10) reported the first Ni-catalyzed Kumada-Tamao type (Mg) 9-23) reaction, in which aryl methyl ether (ArOMe) acted as the electrophilic partner, and this is now recognized as the first example of Ni-catalyzed activation of an inert C-O bond. However, this breakthrough was overlooked for decades, until quite recently. After the development of improved conditions, ArOR can now be used as a coupling partner in several types of transition metal (TM)-catalyzed cross-couplings and related transformations, such as Suzuki-Miyaura-type (B), [24][25][26][27][28][29][30][31] Negishi-type (Zn or Al), [32][33][34][35][36] Murahashi-type (Li), [37][38][39][40] and other reactions. 41-50) As a continuation of our work in this area, we reported in 2012 the first ethereal Negishi-type coupling of aryl alkyl ether 36) (Chart 1(1)) and in 2016 we reported a systematic examination of ethereal Murahashi-type reaction 37) (Chart 1(2)). More recently, we also reported an in-depth study of Ni-catalyzed cross-coupling between organoaluminums and various types of C-O electrophiles, including aryl alkyl ether. 32) Results and DiscussionThe conventional catalytic cycle for cross-coupling reaction consists of three elemental steps: oxidative addition (OA), transmetalation, and reductive elimination. [51][52][53][54] Martin and colleagues reported that direct OA of a E C-O bond to Ni(0) requires high temperature, based on experimental and theoretical findings.46) Computational studies by Nakamura and colleagues, ...

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confidence: 72%

Ethereal C–O Bond Cleavage Mediated by Ni(0)-Ate Complex: A DFT Study

et al. 2017

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“…A remarkable exception was found when employing heteroaromatics as substrates, giving access to valuable heteroaryl amines in good yields. 46 Unfortunately, high catalysts loadings were required to effect the targeted transformation.…”

Section: C-n Bond-forming Reactionsmentioning

confidence: 99%

Metal-catalyzed activation of ethers via C–O bond cleavage: a new strategy for molecular diversity

2014

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In 1979, the seminal work of Wenkert set the standards for the utilization of aryl and vinyl ethers as coupling partners via C-O bond-cleavage. Although the topic remained dormant for almost three decades, the last years have witnessed a renaissance in this area of expertise, experiencing an exponential growth and becoming a significant discipline within the cross-coupling arena. The means to utilize readily accessible aryl or vinyl ethers as counterparts does not only represent a practical, powerful and straightforward alternative to organic halides, but also constitutes an excellent opportunity to improve our chemical knowledge on a relative unexplored area of expertise. This review summarizes the most significant developments in the area of C-O bond-cleavage when employing aryl or vinyl ethers, providing a detailed overview of the current state of the art and including future aspects, when applicable.

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“…One, which was developed by Tobisu and Chatani, is a carbon-nitrogen-forming reaction in which an amine is used as a nucleophile (Eq. 27) [93,94]. Several methoxyarenes and heteroarenes have been reported to be aminated with secondary amines under conditions in which a Ni(0)/IPr catalyst is used.…”

Section: Carbon-heteroatom Bond-forming Reactionsmentioning

confidence: 99%

Nickel-Catalyzed Cross-Coupling Reactions of Unreactive Phenolic Electrophiles via C–O Bond Activation

2016

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Nickel-catalyzed cross-coupling reactions of aryl esters, carbamates, carbonates, ethers and arenols are reviewed. Carbon-oxygen bonds in these phenol derivatives cannot be activated by palladium, a typical cross-coupling catalyst, but a low valent nickel species in conjunction with a strong σ-donor ligand is uniquely effective for achieving this. The review is organized primarily by substrate class and secondarily by coupling partners, encompassing organometallics, heteroatom nucleophiles, C-H bonds and many others. Although the reactions in this category are covered thoroughly, each reaction is described only briefly, so that it is possible to quickly overview the spectrum of nickel-catalyzed cross-coupling reactions of inert phenol derivatives. The robustness of inert phenol derivatives under typically used catalytic conditions as well as their utility as a directing group allow unique synthetic applications of these new C-O cross-coupling reactions, which is also included in cases where appropriate. Mechanistic aspects of C-O bond activation by nickel are also summarized, highlighting their diversity compared with the C-X bond activation involved in conventional cross-coupling processes.

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Ni(0)/NHC-catalyzed amination of N-heteroaryl methyl ethers through the cleavage of carbon‒oxygen bonds

Cited by 91 publications

References 42 publications

Ethereal C–O Bond Cleavage Mediated by Ni(0)-Ate Complex: A DFT Study

Ethereal C–O Bond Cleavage Mediated by Ni(0)-Ate Complex: A DFT Study

Metal-catalyzed activation of ethers via C–O bond cleavage: a new strategy for molecular diversity

Nickel-Catalyzed Cross-Coupling Reactions of Unreactive Phenolic Electrophiles via C–O Bond Activation

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