Nickel‐Catalyzed Stereospecific C−H Coupling of Benzamides with Epoxides

Xu, Shibo; Takamatsu, Kazutaka; Hirano, Koji; Miura, Masahiro

doi:10.1002/ange.201807664

Cited by 7 publications

(2 citation statements)

References 45 publications

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“…The important advantages of such annulation or cyclization reactions is that they can be used in the one-step synthesis of heterocycles that proceed via directed C−H bond activation. As of this writing, a variety of compounds, such as alkynes, 289−305 arynes, 306,307 allenes, 308−312 alkenes, 302,313−317 isonitriles, 318−323 nitriles, 324 nitroalkanes, 325 α-bromoketones, 326 epoxides, 327 carboxylates, 328 acids, or anhydrides 329 have been used as coupling partners in annulation or cyclization reactions of aromatic or aliphatic amides. In addition, a few studies have reported that the cyclization proceeds in an intramolecular manner, leading to the formation of a C−heteroatom bond.…”

Section: Nn-bidentate Directing Groupsmentioning

confidence: 99%

“…325 On the other hand, the use of higher nitroalkanes 326 Hirano and Miura reported the Ni-catalyzed stereospecific synthesis of 3,4-dihydroisocoumarins through the C−H coupling of aromatic amides with epoxides followed by cyclization (Scheme 62d). 327 In 2018, the Ni-catalyzed oxidative decarboxylative annulation of aromatic amides with orthofluoro-substituted (hetero)aromatic carboxylates was developed for the synthesis of phenanthridinone derivatives (Scheme 62e). 328 The reaction involves a sequence of events, including a C−H decarboxylative arylation at the orthoposition of aromatic amides followed by an intramolecular S N Ar reaction in the presence of Na 2 CO 3 at higher temperature, i.e., 130 °C.…”

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Bidentate Directing Groups: An Efficient Tool in C–H Bond Functionalization Chemistry for the Expedient Construction of C–C Bonds

2020

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During the past decades, synthetic organic chemistry discovered that directing group assisted C−H activation is a key tool for the expedient and siteselective construction of C−C bonds. Among the various directing group strategies, bidentate directing groups are now recognized as one of the most efficient devices for the selective functionalization of certain positions due to fact that its metal center permits fine, tunable, and reversible coordination. The family of bidentate directing groups permit various types of assistance to be achieved, such as N,N-dentate, N,O-dentate, and N,S-dentate auxiliaries, which are categorized based on the coordination site. In this review, we broadly discuss various C− H bond functionalization reactions for the formation of C−C bonds with the aid of bidentate directing groups.

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Section: Nn-bidentate Directing Groupsmentioning

confidence: 99%

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Bidentate Directing Groups: An Efficient Tool in C–H Bond Functionalization Chemistry for the Expedient Construction of C–C Bonds

2020

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Exploiting Strained Rings in Chelation Guided C−H Functionalization: Integration of C−H Activation with Ring Cleavage

Shah

Pradhan

et al. 2019

Chemistry An Asian Journal

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Strained ring systemsa re regarded as privileged coupling partnersi nd irected CÀHb ond functionalization and have emergeda sapotential research area in organic synthesis. The inherent ring strain in these systems acts as a driving force, allowing the facile construction of diversified structural scaffolds via integrating CÀHa ctivation and ringscission. The mechanistic underpinnings allows the implementation of ap lethora of CÀHb onds across plentiful or-ganic substrates, including the less reactive alkyl ones. Consideringt he synthetic space, this area will foster developments of novel synthetic methods in chelation guided CÀH functionalization. This review will focus on recent developments in transition-metal catalyzed chelation assisted concomitant CÀHa ctivation and ring scissiono fs trained rings to attain molecular complexity. Figure 1. Strained rings/carbocycles vs. heterocyclic counterparts.[a] Dr.

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Synthesis of Seven‐Membered Benzolactones by Nickel‐Catalyzed C−H Coupling of Benzamides with Oxetanes

Takamatsu

Hirano

et al. 2019

Chemistry A European J

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AN iCl 2 (PEt 3 ) 2 -catalyzed regioselectiveC ÀHc oupling of 8-aminoquinoline-derived benzamides with oxetanes has been developed. The reaction proceeds with concomitant removal of the 8-aminoquinoline auxiliary to directly form the corresponding seven-membered benzolactones, which frequently occur in naturalp roductsa nd bioactive molecules. Additionally,n os tereochemical erosion is observed during the course of the reaction, and the use of enantioenriched and substituted oxetane thus provides an ew avenue to theo ptically active benzolactone.Oxetane constitutes an important class of cyclic ethers in organic synthetic chemistrya nd polymer synthesis. Owing to its high strain energy, [1] it can undergo av ariety of ring-opening reactions with highly reactive organometallic reagents and heteroatomn ucleophilesi nt he presence or absence of Brønsted and Lewis acid promotors to form the corresponding threecarbon homologated, oxygenated products and/or polyethers. [2] However, redox-activet ransition-metal-catalyzed coupling reactions with oxetane are relatively limited, compared to the three-membered analogue, epoxide, probably because of slightly less distortion energy (oxetane:1 07 kJ mol À1 vs. epoxide:1 14 kJ mol À1 ). [1] As an early work, Murai and co-workers developed the rhodium-catalyzed silylformylation of oxetanes with hydrosilanes andc arbon monoxide. [3] Gansäuer also reported the titanocene-catalyzed ring-opening reductive dimerization to provide 1,6-hexanediols. [4] Recently,s ome research groups developed uniquec oupling reactions of oxetanes,i ncluding the rhodium-catalyzed carbene insertion, [5] gold-nanoparticle-catalyzed silaboration, [6] and iron-catalyzed oxidative CÀHc oupling, [7] but synthetic utility of oxetanesu nder transition-metal catalysis still remains underdeveloped.Scheme1.Nickel-catalyzed CÀHc ouplings of quinoline benzamides with epoxides (a) and oxetanes (b).[a] S.

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Nickel‐Catalyzed Stereospecific C−H Coupling of Benzamides with Epoxides

Cited by 7 publications

References 45 publications

Bidentate Directing Groups: An Efficient Tool in C–H Bond Functionalization Chemistry for the Expedient Construction of C–C Bonds

Bidentate Directing Groups: An Efficient Tool in C–H Bond Functionalization Chemistry for the Expedient Construction of C–C Bonds

Exploiting Strained Rings in Chelation Guided C−H Functionalization: Integration of C−H Activation with Ring Cleavage

Synthesis of Seven‐Membered Benzolactones by Nickel‐Catalyzed C−H Coupling of Benzamides with Oxetanes

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