Nickel-catalyzed enantioselective domino Heck/Sonogashira coupling for construction of C(sp)-C(sp) bond-substituted quaternary carbon centers

Chen, Hui; Ai, Zhenkang; Guo, Lin; Yao, Licheng; Li, Yaopeng; Gu, Bing-Lin; Zhang, Yixuan; Liu, Yahu A.; Tian, Boxue; Liao, Xuebin

doi:10.1016/j.tchem.2022.100021

Cited by 5 publications

(7 citation statements)

References 91 publications

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“…The mean Co-C bond length of the four pseudo-equatorial carbonyls is somewhat longer than that of the two pseudo-axial C≡O ligands (1.815(7) vs. 1.789(7) Å). The C2-C3 bond distance of 2 is much shorter than that of a C-C single bond, but considerably elongated with respect to the C≡C bond reported for [phthalimidoCH 2 C≡CCH 2 phthalimido] (CSD refcode ECUFOB) (1.323(9) vs. 1.191(4) Å) [28].…”

Section: Resultsmentioning

confidence: 66%

(µ2-η4-N-(2-Butynyl)phthalimide)(hexacarbonyl)dicobalt

Jourdain

Knorr

Charenton

et al. 2023

Molbank

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The reaction of [Co2(CO)8] with an equimolar amount of the internal alkyne N-(2-butynyl)phthalimide (1-Phthalimido-2-butyne) 1 in heptane solution yields the title compound [Co2(CO)6(µ-phthalimidoCH2C≡CMe)] 2. Compound 2 has been characterized using IR, 1H and 13C NMR spectroscopy; the tetrahedrane-type cluster framework has been ascertained using a single-crystal X-ray diffraction study performed at 100 K.

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Section: Resultsmentioning

confidence: 66%

(µ2-η4-N-(2-Butynyl)phthalimide)(hexacarbonyl)dicobalt

Jourdain

Knorr

Charenton

et al. 2023

Molbank

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“…55,56,58 The activity of a Ni(II) complex toward reductive steps in a catalytic cycle is dramatically influenced by ligand field strength and coordination geometry; 54,59,60 similar considerations were also demonstrated for S = 1 chiral enantioselective Ni(II)−diimine dihalide crosscoupling catalysts. 44,61,62 In addition to redox potentials, the geometric and electronic structures of Ni−bpy complexes determine their light harvesting ability through the molar absorption coefficients of the UV−vis transitions. As a ligand with a significant π-conjugation, the bpy possesses low-lying π*-orbitals capable of backbonding with the metal center.…”

Section: Nickel Electronic Structure Primermentioning

confidence: 99%

Mechanisms of Photoredox Catalysis Featuring Nickel–Bipyridine Complexes

Cagan,

Bím,

Kazmierczak

et al. 2024

ACS Catal.

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Metallaphotoredox catalysis can unlock useful pathways for transforming organic reactants into desirable products, largely due to the conversion of photon energy into chemical potential to drive redox and bond transformation processes. Despite the importance of these processes for cross-coupling reactions and other transformations, their mechanistic details are only superficially understood. In this review, we have provided a detailed summary of various photoredox mechanisms that have been proposed to date for Ni−bipyridine (bpy) complexes, focusing separately on photosensitized and direct excitation reaction processes. By highlighting multiple bond transformation pathways and key findings, we depict how photoredox reaction mechanisms, which ultimately define substrate scope, are themselves defined by the ground-and excitedstate geometric and electronic structures of key Ni-based intermediates. We further identify knowledge gaps to motivate future mechanistic studies and the development of synergistic research approaches spanning the physical, organic, and inorganic chemistry communities.

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“… Subsequent to the first report with aryl bromides in 2018, this versatile method was extended to various coupling partners, including carbon dioxide and alkene, yielding indolone derivatives with all-carbon quaternary stereocenters ( 10 – 11 ). The Liao group expanded this protocol to the terminal alkyne as a viable coupling partner . While bipyridine ligands also showed activity in these reactions, ferrocenyl-PHOX ligand ( S , S p )- L13 was favored for its superior reactivity and enantioselectivity.…”

Section: Ni/pn-catalyzed Cross-couplingsmentioning

confidence: 99%

“…The Liao group expanded this protocol to the terminal alkyne as a viable coupling partner. 49 While bipyridine ligands also showed activity in these reactions, ferrocenyl-PHOX ligand (S,S p )-L13 was favored for its superior reactivity and enantioselectivity. The presence of the ferrocene skeleton was found to be critical, as other PHOX-type ligands typically displayed significantly lower reactivity and selectivity.…”

Section: Cross-electrophile Couplingmentioning

confidence: 99%

P,N Ligand in Ni-Catalyzed Cross-Coupling Reactions: A Promising Tool for π-Functionalization

Bae,

Cho

2023

ACS Catal.

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Bidentate P,N ligands, integrating phosphine and nitrogen donors, are highlighted for their versatile characteristics, offering both electronic and steric tunability. Their hemilabile nature, coupled with the ability to modulate both electronic and steric properties through the choice of donor atoms and substituents, has expanded the horizons of chemical transformations. This Review focuses on Nicatalyzed cross-coupling reactions mediated by P,N ligands. The asymmetrical nature of P,N ligands, with each donor atom playing a specific role in the catalytic cycle, offers control, stability, and unique regioselectivity in catalytic processes. In particular, the Ni/P,N-catalytic system exhibits remarkable reactivity with πsubstrates including alkenes, alkynes, and allenes. A thorough mechanistic understanding of these processes offers insights into the trends and future directions in Ni/P,N-catalyzed cross-coupling reactions.

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Nickel-catalyzed enantioselective domino Heck/Sonogashira coupling for construction of C(sp)-C(sp) bond-substituted quaternary carbon centers

Cited by 5 publications

References 91 publications

(µ2-η4-N-(2-Butynyl)phthalimide)(hexacarbonyl)dicobalt

(µ2-η4-N-(2-Butynyl)phthalimide)(hexacarbonyl)dicobalt

Mechanisms of Photoredox Catalysis Featuring Nickel–Bipyridine Complexes

P,N Ligand in Ni-Catalyzed Cross-Coupling Reactions: A Promising Tool for π-Functionalization

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