Recent Advances in the Construction of Fluorinated Organoboron Compounds

Ma, Xingxing; Kuang, Zhijie; Song, Qiuling

doi:10.1021/jacsau.1c00129

Cited by 22 publications

(10 citation statements)

References 142 publications

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“…Developing catalytic methods to incorporate fluorinated subunits into organoboron compounds is a key interest in the contemporary research area owing to its potential pharmaceutical, agrochemical, and material applications. [1] The chiral CF 3 motif is a privileged substructure found in various drug candidates, such as Odanacatib, [2] Telotristat, [3] and Bitopertin [4] (Figure 1 a). Further, the boron bound carbon stereocenters is an integral part of clinically approved anticancer drugs [5] such as Bortezomib [6] and Ixazomib [7] (Figure 1 b).…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Organocatalytic Homologation: Access to Diverse Chiral Trifluoromethyl Organoboron Species

Jayarajan

Kireilis

Eriksson

et al. 2022

Chemistry A European J

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A broad range of aliphatic, aromatic, and heterocyclic boronic acids were successfully homologated using trifluorodiazoethane in the presence of BINOL derivatives to provide the corresponding chiral trifluoromethyl containing boronic acid derivatives in high yields and excellent enantioselectivity. The in situ conversion of the chiral transient boronic acids to the corresponding alcohols or β‐CF3 carboxylates are also demonstrated.

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Section: Introductionmentioning

confidence: 99%

Asymmetric Organocatalytic Homologation: Access to Diverse Chiral Trifluoromethyl Organoboron Species

Jayarajan

Kireilis

Eriksson

et al. 2022

Chemistry A European J

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“…Nevertheless, compared with vast reports on their constructions, deconstructive functionalizations of fluorine-containing molecules, especially the development of unusual transformations of C–F bonds are relatively sparce largely owing to the inertness and stability of C–F bond . As a result, precisely deconstructive functionalizations of organofluorine compounds become very important and thus have gained significant attentions in chemical community . Difluorocarbene, one of the most important and powerful fluorine-containing synthons, could be readily accessible from various commercially available and inexpensive halodifluoroalkyl reagents.…”

Section: Introductionmentioning

confidence: 99%

Unconventional Transformations of Difluorocarbene with Amines and Ethers

Song

2023

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS: Fluorine-containing compounds are extensively involved in various fields originating from intriguing and unique characteristics of fluorine atom; notably, in pharmaceuticals, the involvement of a fluorine atom or a fluorine-containing group is a chief technique for improving the pesticide effect and developing new drugs. Difluorocarbene, one of the most important and powerful fluorine-containing reagents, is widely employed and studied in many areas mainly to assemble gem-difluoromethyl molecules, including but not limited to the abundant reactions between difluorocarbene with nucleophilic substrates, Wittig reaction with ketones or aldehydes, cascade reaction with both a nucleophile and an electrophile, or [2+1] cycloaddition with alkenes or alkynes. However, its unconventional and intriguing protocols beyond as a difluoromethyl synthon have rarely been studied, and thus, it is highly desired given its abundance, inexpensiveness and peculiar properties. In this Account, we mainly discuss our discovery with unconventional transformations of difluorocarbene, instead of as a sole difluoromethyl source (different from other dihalocarbene), actually can serve as an electron acceptor to activate C−X bonds (X = N and O) and thus promote a myriad of fascinating transformations for the assembly of versatile valuable products with various aza-compounds (primary/secondary/tertiary amines as well as NH 3 and NaNH 2 and so on) and aliphatic ethers in the absence of transition metals and expensive ligands. Inspired by the electron-deficient characteristics of difluorocarbene, we first found that the isocyanides could be readily formed in situ when the unoccupied orbital of difluorocarbene meets the lone-pair of primary amines; in basic condition, a cascade defluorination and cyclizations could afford plethora of valuable N-containing heterocycles.Meanwhile, we disclosed that cyano anion could be accessible in situ as well when difluorocarbene and NaNH 2 or NH 3 were mixed up in suitable basic conditions, and thus a series of aryl nitrile compounds were obtained in the presence of Pd catalysis and ArI. Interestingly, when difluorocarbene encountered secondary amines, formamides were rendered under mild reactions. Of note, concomitant functionalizations of C and N moieties via cleavage of the unstrained C(sp 3 )−N bond in the absence of metal and oxidant are sparce, which indeed significantly add versatility and diversity to products. Gratifyingly, by uitilizing difluorocarbene and cyclic tertiary amines, we achieved difluorocarbene-mediated deconstructive functionalizations for the first time, showing successive C(sp 3 )−N bond scission of amines and simultaneous functionalization of C and N atoms which would be introduced into the products in the absence of transition metals and oxidants. This method provides a brand-new while very universal synthetic pathway to selectively cleave inert unactivated Csp 3 −N bonds, in which halodifluoromethyl reagents act as both C1 synthon and...

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“…2 More recently, fluorinated organoboron compounds have emerged as unique building blocks with potential applications. 3 The installation of fluorine in organic molecules can significantly enhance their properties and bioactivities for useful applications in pharmaceuticals, agrochemicals, and functional materials. 4 The transition-metal-catalyzed C−F bond activation strategy can allow access to fluorine-containing organoboron compounds through selective monodefluoroborylation of polyfluorinated substrates.…”

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confidence: 99%

Palladium-Catalyzed Stereoselective Defluoroborylation of gem-Difluoroalkenes with Unsymmetrical Diboron: Access to Tetrasubstituted Monofluorinated Vinyl–B(dan) Derivatives

2023

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The stereoselective C–F bond borylation of tetrasubstituted β,β-difluoroacrylates has been achieved. In contrast to the previously used B2pin2 reagent, which only led to dimerization products, this work employs the unsymmetrical diboron reagent (pin)B–B(dan) under the palladium(0)-catalyzed conditions to access novel boronamides containing the monofluorinated vinyl–B(dan) functionality. These compounds can cross-couple directly with gem-difluoroalkenes without reactivation in Suzuki–Miyaura reactions to afford vincinal difluoro 1,3-dienes with modular control of the substituents.

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Recent Advances in the Construction of Fluorinated Organoboron Compounds

Cited by 22 publications

References 142 publications

Asymmetric Organocatalytic Homologation: Access to Diverse Chiral Trifluoromethyl Organoboron Species

Asymmetric Organocatalytic Homologation: Access to Diverse Chiral Trifluoromethyl Organoboron Species

Unconventional Transformations of Difluorocarbene with Amines and Ethers

Palladium-Catalyzed Stereoselective Defluoroborylation of gem-Difluoroalkenes with Unsymmetrical Diboron: Access to Tetrasubstituted Monofluorinated Vinyl–B(dan) Derivatives

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