Reactions of diheteroaryl sulfoxides with heteroaryllithiums?ligand coupling and exchange reactions

Inubushi, Yoichi; Yoshihara, Masakuni; Ōae, Shigeru

doi:10.1002/(sici)1098-1071(199610)7:5<299::aid-hc4>3.0.co;2-7

Cited by 8 publications

(4 citation statements)

References 24 publications

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“…2‐(Furan‐2‐yl)pyridine (6 g) :32 Colorless liquid; 1 H NMR (CDCl 3 , 300 MHz): δ =6.53 (m, 1 H), 7.06 (d, J =3.3 Hz, 1 H), 7.15 (m, 1 H), 7.53 (m, 1 H), 7.70 (m, 2 H), 8.60 ppm (d, J =3.8 Hz, 1 H); 13 C NMR (CDCl 3 , 75 MHz): δ =108.5, 111.9, 118.5, 121.8, 136.5, 143.2, 149.2, 149.5, 153.4 ppm.…”

Section: Methodsmentioning

confidence: 99%

Deprotonative Metalation of Substituted Benzenes and Heteroaromatics Using Amino/Alkyl Mixed Lithium–Zinc Combinations

Snégaroff

Komagawa

Chevallier

et al. 2010

Chemistry A European J

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Different homoleptic and heteroleptic lithium–zinc combinations were prepared, and structural elements obtained on the basis of NMR spectroscopic experiments and DFT calculations. In light of their ability to metalate anisole, pathways were proposed to justify the synergy observed for some mixtures. The best basic mixtures were obtained either by combining ZnCl2⋅TMEDA (TMEDA=N,N,N′,N′‐tetramethylethylenediamine) with [Li(tmp)] (tmp=2,2,6,6‐tetramethylpiperidino; 3 equiv) or by replacing one of the tmp in the precedent mixture with an alkyl group. The reactivity of the aromatic lithium zincates supposedly formed was next studied, and proved to be substrate‐, base‐, and electrophile‐dependent. The aromatic lithium zincates were finally involved in palladium‐catalyzed cross‐coupling reactions with aromatic chlorides and bromides.

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Section: Methodsmentioning

confidence: 99%

Deprotonative Metalation of Substituted Benzenes and Heteroaromatics Using Amino/Alkyl Mixed Lithium–Zinc Combinations

Snégaroff

Komagawa

Chevallier

et al. 2010

Chemistry A European J

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“…Through a series of reports, Oae, Furukawa, and co-workers realized that heteroaromatic sulfoxides 110 , in particular 2-pyridyl sulfoxides, were efficient scaffolds for ligand coupling (Scheme ). − The substituent (i.e., R group) attached to the sulfur atom of the sulfoxide 110 and the identity of the organometallic reagent (either a Grignard or an organolithium reagent) 111 were tuned for each particular coupling. This route enabled the preparation of a range unsymmetric bipyridines ( 112a – d ) and was also extended to couplings with other hetero (to give 112e )- and nonheteroaromatic (to give 112f , g ) organometallic reagents.…”

Section: Sulfur(iv) Reagents In Ligand Coupling For Biaryl Synthesismentioning

confidence: 99%

Sulfur(IV) in Transition-Metal-Free Cross-Couplings for Biaryl Synthesis

Perry

Yorimitsu

2022

ACS Sustainable Chem. Eng.

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The reactivity of sulfur(IV) compounds is of great current interest among organic chemists. In this Perspective, we discuss the chemistry of sulfur(IV) (namely, sulfoxides, sulfonium salts, and sulfinates) within the area of transition-metal-free cross-couplings for biaryl synthesis. These sulfur(IV)-based methods show potential in sustainable biaryl formation and can deliver unique biaryl structures that are difficult to access by other means. This Perspective also highlights how the versatile reactivity of sulfur(IV) has helped design new reagents, mediators, and catalysts.

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“…Active CÀ H bonds vicinal to C-SO 2 bonds exhibit a high stability in this reaction (4 and 75-79). Potentially reactive functionalities are also tolerated, such as hydroxyl group at the βposition of fluoroalkyls (83)(84)(85)(86)(87)(88)(89)(90)(91)(92)(93)(94), the deprotonated form of which would readily take part in Smiles rearrangements at room temperature. [40b] In our hand, only the extremely sterically hindered alcohol was detected to undergo such a Angewandte Chemie reaction to some extent (89), [41] probably due to a relatively slow attack on sulfone by the Grignard reagent, and protection of the hydroxyl group led to an immediate and productive coupling (90).…”

Section: Substrate Scope and Synthetic Applicationsmentioning

confidence: 99%

N‐Heteroaromatic Fluoroalkylation through Ligand Coupling Reaction of Sulfones

Liang,

Wang,

Zhou

et al. 2024

Angew Chem Int Ed

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Ligand coupling on hypervalent main group elements has emerged as a pivotal methodology for the synthesis of functionalized N‐heteroaromatic compounds in recent years due to the avoidance of transition metals and the mildness of the reaction conditions. In this direction, the reaction of N‐heteroaryl sulfur(IV) and N‐heteroaryl phosphorus(V) compounds has been well studied. However, the ligand coupling of sulfur(VI) is still underdeveloped and the reaction of alkyl N‐heteroarylsulfones is still elusive, which does not match the high status of sulfones as the chemical chameleons in organic synthesis. Here we present a ligand coupling‐enabled formal SO2 extrusion of fluoroalkyl 2‐azaheteroarylsulfones under the promotion of Grignard reagents, which not only enriches the chemistry of sulfones, but also provides a novel and practical synthetic tool towards N‐heteroaromatic fluoroalkylation.

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Reactions of diheteroaryl sulfoxides with heteroaryllithiums?ligand coupling and exchange reactions

Cited by 8 publications

References 24 publications

Deprotonative Metalation of Substituted Benzenes and Heteroaromatics Using Amino/Alkyl Mixed Lithium–Zinc Combinations

Deprotonative Metalation of Substituted Benzenes and Heteroaromatics Using Amino/Alkyl Mixed Lithium–Zinc Combinations

Sulfur(IV) in Transition-Metal-Free Cross-Couplings for Biaryl Synthesis

N‐Heteroaromatic Fluoroalkylation through Ligand Coupling Reaction of Sulfones

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