Recent Developments in Negishi Cross-Coupling Reactions

Haas, Diana; Hammann, Jeffrey M.; Greiner, Robert; Knöchel, Paul

doi:10.1021/acscatal.5b02718

Cited by 361 publications

(199 citation statements)

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“…[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.…”

Section: Resultsmentioning

confidence: 99%

“…[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, 55) Liu and colleagues, 56) Martin and colleagues, 46) and us 14) clearly demonstrated that OA of a E C-O bond generally involves a very high activation barrier (Chart 2(1)), even considering the Lewis acidity of Mg (Chart 2 (2)).…”

Section: Resultsmentioning

confidence: 99%

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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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“…[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.…”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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

et al. 2017

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“…The reaction was found to tolerate a number of functional groups on the aryl electrophile, thanks to the mild basic and nucleophilic character of organozinc compounds. [22] Some substituted Boc-piperidines also gave rise to the α-and β-arylated products was obtained, from which the β-arylated product 11b1 was isolated in 40% yield. Replacing the pyrrole subunit of the ligand with imidazole and further decreasing the bulk around the phosphorus atom by replacing the isopropyl with isobutyl groups led to ligand L 5 , which provided an improved selectivity of 85:15 in favor of the β-isomer, together with a yield of 63%.…”

Section: Normal and Migrative Arylation Of Boc-aminesmentioning

confidence: 98%

Selectivity Control in the Palladium-catalyzed Cross-coupling of Alkyl Nucleophiles

Baudoin¹

2016

Chimia

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Site-selectivity remains a major challenge in metal-catalyzed C-H bond functionalization. Most existing strategies rely on the introduction of a directing group or on the intrinsic reactivity of the substrate. In this account article, we describe the development of an alternative strategy based on the migration of an organopalladium species along an alkyl chain, wherein the phosphine ligand controls the cross-coupling site. This concept was first implemented with lithium enolates, and then extended to α-zincated alkylamines obtained by directed lithiation and transmetalation. Both the direct and the migrative cross-couplings, which are controlled by simply switching the ligand, furnish synthetically useful organic intermediates.

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“…In analogy to the venerable Negishi reaction, 14 oxidative addition of palladium(0) complex A into a silyl iodide would generate intermediate B . Transmetallation with an alkyl organ-ometallic reagent to form C , followed by rapid reductive elimination, leads to the desired alkyl silane and regeneration of the catalyst.…”

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confidence: 99%