Decarboxylative functionalization of cinnamic acids

Borah, Arun Jyoti; Yan, Guobing

doi:10.1039/c5ob00727e

Cited by 101 publications

(37 citation statements)

References 159 publications

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“…[22] Ther eaction is scalable,a nd little diminution of yield was observed in gram-scale difluoromethylation of 2a. [22] Ther eaction is scalable,a nd little diminution of yield was observed in gram-scale difluoromethylation of 2a.…”

Section: Angewandte Chemiementioning

confidence: 99%

Palladium‐Catalyzed Decarbonylative Difluoromethylation of Acid Chlorides at Room Temperature

2018

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Methods for the direct synthesis of difluoromethylated arenes are sparse,d espite the importance of the difluoromethyl group in medical, agro-, and materials chemistry.A palladium-catalyzed decarbonylative cross-coupling reaction of acid chlorides with adifluoromethyl zinc reagent is achieved to access difluoromethylated compounds.T he transformation proceeds at room temperature and shows broad functional group tolerance,thus providing ageneral and efficient method for decarbonylative difluoromethylation of aw ide range of aromatic carboxylica cids.Scheme 1. Recent developments in catalyticd ifluoromethylation protocol and novel decarbonylative approach.

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Section: Angewandte Chemiementioning

confidence: 99%

Palladium‐Catalyzed Decarbonylative Difluoromethylation of Acid Chlorides at Room Temperature

2018

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“…Zuschriften trifluoromethyl (2p), and amide (2s)g roups.B asic heterocycles,o ften considered al iability in transition metal catalyzed coupling reactions,a re well tolerated in the present reaction, with substrates containing pyrazole (2n), oxadiazole (2q), and quinoxaline (2r)r ings furnishing high difluoromethylation yields.I na ddition to aroyl chlorides, a,b-unsaturated acid chlorides can serve as electrophiles,y ielding difluoromethylalkenes (2t). [22] Ther eaction is scalable,a nd little diminution of yield was observed in gram-scale difluoromethylation of 2a.…”

Section: Angewandte Chemiementioning

confidence: 99%

Palladium‐Catalyzed Decarbonylative Difluoromethylation of Acid Chlorides at Room Temperature

2018

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Methods for the direct synthesis of difluoromethylated arenes are sparse,d espite the importance of the difluoromethyl group in medical, agro-, and materials chemistry.A palladium-catalyzed decarbonylative cross-coupling reaction of acid chlorides with adifluoromethyl zinc reagent is achieved to access difluoromethylated compounds.T he transformation proceeds at room temperature and shows broad functional group tolerance,thus providing ageneral and efficient method for decarbonylative difluoromethylation of aw ide range of aromatic carboxylica cids. Scheme 1. Recent developments in catalyticd ifluoromethylation protocol and novel decarbonylative approach.

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“…Them ethod was also applicable to the decarbonylative borylation of alkenyl and alkyl thioesters,e xpanding the range of available compounds (Table 2C). [22] While soft nucleophiles such as thiols easily react with a,b-unsaturated thioesters to form 1,4-adducts,4 -methoxycinnamic acid S-ethyl ester (2ai)w as transformed to alkenylboronic ester 3ai in high yield under the same conditions.F urthermore, although not fully optimized, the borylative cleavage of aC(sp 3 )ÀCbond in 2aj also proceeded to afford alkylboronic ester 3aj by the use of cesium fluoride as ab ase instead of KOAc. [11] We currently anticipate that the borylative C À Cb ond cleavage of thioester 2 proceeds by the decarbonylation of acyl(boryl)rhodium(III) species V,a swe initially envisioned (Scheme 2A).…”

Section: Angewandte Chemiementioning

confidence: 99%

Rhodium‐Catalyzed Decarbonylative Borylation of Aromatic Thioesters for Facile Diversification of Aromatic Carboxylic Acids

Ochiai¹,

Uetake²,

Niwa³

et al. 2017

Angewandte Chemie

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Transformation of aromatic thioesters into arylboronic esters was achieved efficiently using ar hodium catalyst. The broad functional-group tolerance and mild conditions of the method have allowed for the two-step decarboxylative borylation of aw ide range of aromatic carboxylic acids,including commercially available drugs.The carboxylic acid is afundamental functional group often found in abroad range of organic molecules,including natural products,p harmaceuticals,a grochemicals,a nd functional materials.The availability of carboxylic acids has been further increased by recent advances in carboxylation reactions.[1] In line with the increasing availability of carboxylic acids,t heir direct decarboxylative functionalization, which significantly expands the diversity of synthesizable molecules,h as also been attracting considerable interest.[2] One of the most straightforward approaches for facile diversification is to transform carboxylic acids into multitransformable intermediates such as organoboron compounds,w hich serve as versatile synthetic intermediates demonstrating aw ide spectrum of reactivities (Scheme 1A).[3] Indeed, recent studies, [4][5][6][7][8][9][10] including ours, [9b, 10a] on catalytic borylative transformations by cleavage of stable bonds,s uch as CÀH, [5] CÀO, [6] CÀN, [7] CÀCN, [8] CÀF, [9] and CÀS [10] bonds,h ave confirmed the validity of this approach. Herein, we report ad ecarbonylative borylation of aromatic thioesters that enabled two-step decarboxylative borylation of aromatic carboxylic acids.Thechallenge of this transformation was to cleave astable C(aromatic)ÀC(carbonyl) bond while forming an easily transformable CÀBb ond. Although various transition-metalcatalyzed decarboxylative transformations of aromatic carboxylic acids have been reported, [2] these transformations were achieved at elevated temperature (typically > 150 8 8C), which greatly limits the scope of applicable substrates.[11] This is probably because al arge amount of energy is required to cleave the stable CÀCb ond. To achieve the CÀCb ond cleavage under milder conditions,w ef ocused on transitionmetal-mediated decarbonylation by acylmetal species I (Scheme 1B).[12] We anticipated that reverse insertion of acarbonyl group in I could smoothly occur by the cleavage of the CÀCb ond under mild conditions to afford arylmetal species II, [2a, 13] which could react with adiboron compound to furnish the borylated product 3.[10a] Recently,S hi et al. and Rueping et al. independently reported nickel-catalyzed decarbonylative borylations based on this approach using esters and amides as precursors for the acylmetal species. However,t hese reactions still required high temperature (> 150 8 8C) with moderate substrate scope. [14] We envisioned that thioester 2,which is astable carboxylic acid derivative, [15] would be abetter precursor of the acylmetal species I because highly chemoselective cleavage of aC (carbonyl) À Sb ond in thioester 2 by oxidative addition to al ow-valent transition metal was anticipated to ...

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Decarboxylative functionalization of cinnamic acids

Cited by 101 publications

References 159 publications

Palladium‐Catalyzed Decarbonylative Difluoromethylation of Acid Chlorides at Room Temperature

Palladium‐Catalyzed Decarbonylative Difluoromethylation of Acid Chlorides at Room Temperature

Palladium‐Catalyzed Decarbonylative Difluoromethylation of Acid Chlorides at Room Temperature

Rhodium‐Catalyzed Decarbonylative Borylation of Aromatic Thioesters for Facile Diversification of Aromatic Carboxylic Acids

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