Iridium-catalyzed B–H insertion of sulfoxonium ylides and borane adducts: a versatile platform to α-boryl carbonyls

Zhang, Shang‐Shi; Xie, Hongmei; Shu, Bing; Che, Tong; Wang, Xiaotong; Peng, Dongming; Yang, Fan; Zhang, Luyong

doi:10.1039/c9cc08795h

Cited by 70 publications

(28 citation statements)

References 62 publications

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“…Theturnover number reached 14 300, which, to our knowledge,isthe highest turnover number reported for aB À Hb ond insertion reaction promoted by am olecular catalyst. [23][24][25][26][27][28][29][30][31][32][33][42][43][44][45][46][47][48] Furthermore,b orane (S)-3ra could easily be converted into widely used boron reagents:c hiral boronic ester 4,p otassium trifluoroborate 5,a nd MIDA( methyliminodiacetic acid) borate 6 (Scheme 3B). Interestingly,w e accidentally discovered that reaction of (S)-3ra with Nchlorosuccinimide resulted in an early quantitative yield of unprecedented chlorinated boron 7.I na ddition, (S)-3ra could be transformed to alcohol 8 by oxidation with H 2 O 2 ,to dibenzylic amine 9 via apotassium trifluoroborate intermediate in one pot, [49] and to chiral triaryl methanes 10 and 11 by means of sp 2 -sp 3 coupling reactions.…”

Section: Resultsmentioning

confidence: 99%

Dirhodium‐Catalyzed Enantioselective B−H Bond Insertion of gem‐Diaryl Carbenes: Efficient Access to gem‐Diarylmethine Boranes

Zhao

et al. 2021

Angewandte Chemie

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The scarcity of reliable methods for synthesizing chiral gem-diarylmethine borons limits their applications. Herein, we report am ethod for highly enantioselective dirhodium-catalyzed B À Hbond insertion reactions with diaryl diazomethanes as carbene precursors.These reactions afforded chiral gem-diarylmethine borane compounds in high yield (up to 99 %y ield), high activity (turnover numbers up to 14 300), high enantioselectivity (up to 99 %e e) and showed unprecedented broad functional group tolerance.T he borane compounds synthesized by this method could be efficiently transformed into diaryl methanol, diaryl methyl amine,a nd triaryl methane derivatives with good stereospecificity.M echanistic studies suggested that the borane adduct coordinated to the rhodium catalyst and thus interfered with decomposition of the diazomethane,a nd that insertion of ar hodium carbene (generated from the diaryl diazomethane) into the B À Hb ond was most likely the rate-determining step.Scheme 1. Methodsf or synthesis of chiral gem-diarylmethine boron compounds.

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Section: Resultsmentioning

confidence: 99%

Dirhodium‐Catalyzed Enantioselective B−H Bond Insertion of gem‐Diaryl Carbenes: Efficient Access to gem‐Diarylmethine Boranes

Zhao

et al. 2021

Angewandte Chemie

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“…Since transition-metalcatalyzed insertion of carbenes into B-H bonds was first disclosed in 2013, it has become a good method for the construction of C-B bonds. [7][8][9][10] When diazo compounds, [11][12][13][14][15][16][17] alkynes, [18][19] or sulfoxonium ylides [20][21] are used as carbene precursors, this method enables the construction of many novel organoboranes in high yields with high regioselectivity and, in some cases, high enantioselectivity (Scheme 1a). Quite recently, insertion of unsaturated carbenes into B-H bonds has also been established as a method for constructing C(sp 2 )-B bonds.…”

Section: Introductionmentioning

confidence: 99%

Copper-Catalyzed Ring-Opening/Borylation of Cyclopropenes

et al. 2022

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Because organoboron compounds readily undergo a diverse array of transformations and are widely used in various fields, the development of C-Bbond-forming reactions have attracted considerable attention. Herein we report a new method for forming C-B bonds by means of Cucatalyzed ring-opening/borylation reactions of cyclopropenes. This method provides efficient access to a new type of stable allylborane-Lewis base adduct, which is a versatile synthon. The configuration of the products can be well controlled with this method, and some of the configurations we obtained are inaccessible by means of other catalytic methods for generating allylborons. Mechanistic studies indicated that the reactions proceed via insertion of an alkenyl Cu carbene-generated in situ by cyclopropene ring opening-into the B-H bond; the ring-opening step determines both the rate and the stereochemistry.

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“…Based on our ongoing research interest in new reactions to β‐keto sulfoxonium ylides and previous work . We herein disclosed the effective Cp*Ir III ‐catalyzed [4+2] annulation of β‐keto sulfoxonium ylides with various 1,2‐diaminoarenes to furnish monosubstituted quinoxaline and its derivatives elegantly through tandem cyclization strategy (Scheme c).…”

Section: Methodsmentioning

confidence: 97%

Iridium‐Catalyzed [4+2] Annulations of β‐Keto Sulfoxonium Ylides and o‐Phenylenediamines: Mild and Facile Synthesis of Quinoxaline Derivatives

et al. 2020

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A synthetic method for quinoxaline derivatives from the [4+2] annulation of β‐keto sulfoxonium ylides and o‐phenylenediamine by using (Cp*IrCl2)2 catalyst is described. This novel protocol features mild reaction conditions, moderate to excellent yields, wide substrate scope, and high functional‐group compatibility. Moreover, this cyclization strategy was successfully applied in late‐stage modification for structurally complex bioactive compounds.

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Iridium-catalyzed B–H insertion of sulfoxonium ylides and borane adducts: a versatile platform to α-boryl carbonyls

Abstract: Iridium-catalyzed boron–hydrogen bond insertion reactions of trimethylamine-borane and sulfoxonium ylides have been demonstrated, furnishing α-boryl ketones in moderate to excellent yields in most cases (51 examples; up to 84%).

Cited by 70 publications

References 62 publications

Dirhodium‐Catalyzed Enantioselective B−H Bond Insertion of gem‐Diaryl Carbenes: Efficient Access to gem‐Diarylmethine Boranes

Dirhodium‐Catalyzed Enantioselective B−H Bond Insertion of gem‐Diaryl Carbenes: Efficient Access to gem‐Diarylmethine Boranes

Copper-Catalyzed Ring-Opening/Borylation of Cyclopropenes

Iridium‐Catalyzed [4+2] Annulations of β‐Keto Sulfoxonium Ylides and o‐Phenylenediamines: Mild and Facile Synthesis of Quinoxaline Derivatives

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