Suzuki Coupling of Amides <i>via</i> Palladium‐Catalyzed C–N Cleavage of <i>N</i>‐Acylsaccharins

Wu, Huan; Li, Yue; Cui, Ming; Jian, Junsheng; Zhang, Zhuo

doi:10.1002/adsc.201600555

Cited by 71 publications

(29 citation statements)

References 57 publications

(2 reference statements)

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“…N-Acylsaccharins are of interest as bench-stable, highly reactive, and easily prepared amides from low-costing saccharin (Scheme 23A) [73]. Independently, Zeng and co-workers reported acyl Suzuki cross-coupling of N-acylsaccharins [74]. We have also explored the activating effect of the mesyl group and found it to be advantageous to the synthesis of biaryl ketones using highly atom-economical mesyl activation (Scheme 23B) [75].…”

Section: Suzuki Cross-coupling Of Amidesmentioning

confidence: 99%

Recent Advances in Acyl Suzuki Cross-Coupling

2019

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Acyl Suzuki cross-coupling involves the coupling of an organoboron reagent with an acyl electrophile (acyl halide, anhydride, ester, amide). This review provides a timely overview of the very important advances that have recently taken place in the acylative Suzuki cross-coupling. Particular emphasis is directed toward the type of acyl electrophiles, catalyst systems and new cross-coupling partners. This review will be of value to synthetic chemists involved in this rapidly developing field of Suzuki cross-coupling as well as those interested in using acylative Suzuki cross-coupling for the synthesis of ketones as a catalytic alternative to stoichiometric nucleophilic additions or Friedel-Crafts reactions.

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Section: Suzuki Cross-coupling Of Amidesmentioning

confidence: 99%

Recent Advances in Acyl Suzuki Cross-Coupling

2019

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“…The experimental data shows the unique activity of N ‐acylsaccharins ( 4 a ) in this transformation. An electron‐withdrawing sulfonyl moiety and distortion of the amide bond might result in ground‐state destabilization of N ‐acylsaccharins, which could explain its high reactivity in this reaction [20d,26] …”

Section: Methodsmentioning

confidence: 99%

A Strategy for Accessing Aldehydes via Palladium‐Catalyzed C−O/C−N Bond Cleavage in the Presence of Hydrosilanes

Wang

et al. 2020

Adv Synth Catal

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We report the catalytic reduction of both active esters and amides by selective C(acyl)À X (X=O, N) cleavage to access aldehyde functionality via a palladium-catalyzed strategy. Reactions are promoted by hydrosilanes as reducing reagents with good to excellent yields and with excellent chemoselectivity for C(acyl)À N and C(acyl)À O bond cleavage. Carboxylic acid C(acyl)À O bonds are activated by 2-chloro-4,6-dimethoxy-1,3,5-triazine (CDMT) to form triazine ester intermediates, which further react with hydrosilanes to yield aldehydes in one-pot two-step procedures. We demonstrate that C (acyl)À O cleavage/formylation offers higher yields and broader substrate scopes compared with C (acyl)À N cleavage under the same reaction conditions.

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“…To date, a wide range of amides and amide-based reagents, including the most reactive N-acyl-glutarimides [13] as well as anilides [14], N-Boc-carbamates [15], N-Ts-sulfonamides [16], N, N-di-Boc amides [17], N-acyl-saccharins [18,19], N-Ms-sulfonamides [20], N-acyl-pyrroles [21], N-Me-pyrimidines [22], N-acyl-succinimides [23][24][25], and N-Ac-amides [26] have been successfully engaged as electrophilic cross-coupling partners by N-C activation. In all examples described to date, the reactivity has been controlled by a ground-state destabilization mechanism of the amide bond [12].…”

Section: Introductionmentioning

confidence: 99%

N-Acylphthalimides: Efficient Acyl Coupling Reagents in Suzuki–Miyaura Cross-Coupling by N–C Cleavage Catalyzed by Pd–PEPPSI Precatalysts

2019

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We report a general, highly selective method for Suzuki–Miyaura cross-coupling of N-acylphthalimides via N–C(O) acyl cleavage catalyzed by Pd–PEPPSI-type precatalysts. Of broad synthetic interest, the method introduces N-acylphthalimides as new, bench-stable, highly reactive, twist-controlled, amide-based precursors to acyl-metal intermediates. The reaction delivers functionalized biaryl ketones by acylative Suzuki–Miyaura cross-coupling with readily available boronic acids. Studies demonstrate that cheap, easily prepared, and broadly applicable Pd–PEPPSI-type precatalysts supported by a sterically demanding IPr (1,3-Bis-(2,6-diisopropylphenyl)imidazol-2-ylidene) ancillary ligand provide high yields in this reaction. Preliminary selectivity studies and the effect of Pd–N-heterocyclic carbenes (NHC) complexes with allyl-type throw-away ligands are described. We expect that N-acylphthalimides will find significant use as amide-based acyl coupling reagents and cross-coupling precursors to acyl-metal intermediates.

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Suzuki Coupling of Amides via Palladium‐Catalyzed C–N Cleavage of N‐Acylsaccharins

Cited by 71 publications

References 57 publications

Recent Advances in Acyl Suzuki Cross-Coupling

Recent Advances in Acyl Suzuki Cross-Coupling

A Strategy for Accessing Aldehydes via Palladium‐Catalyzed C−O/C−N Bond Cleavage in the Presence of Hydrosilanes

N-Acylphthalimides: Efficient Acyl Coupling Reagents in Suzuki–Miyaura Cross-Coupling by N–C Cleavage Catalyzed by Pd–PEPPSI Precatalysts

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