1,3-Carboboration of iodonium ylides

Gazis, Theodore A.; Thaker, Bayan A J Mohajeri; Willcox, Darren; Ould, Darren M. C.; Wenz, Jan; Rawson, Jeremy M.; Hill, Michael S.; Wirth, Thomas; Melen, Rebecca L.

doi:10.1039/c9cc08749d

Cited by 15 publications

(6 citation statements)

References 25 publications

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“…A limitation of this reaction was that cyclic iodonium ylides (e. g., 1 c , 1 d ) failed to produce any of the desired O−H insertion products in all attempts. This result is consistent with such ylides being inherently more stable than their acyclic counterparts, [42] possibly due to better anionic stabilization by the planar β‐dicarbonyl motif, or due to secondary bonding between this motif and iodine [43] …”

Section: Resultssupporting

confidence: 81%

σ‐Holes in Iodonium Ylides: Halogen‐Bond Activation of Carboxylic Acids, Phenols and Thiophenols May Enable Their X−H Insertion Reactions

Montgomery

Jameel

Cuzzucoli

et al. 2022

Chemistry A European J

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The first systematic evaluation of the electrostatic potential energy maps of iodonium ylides was conducted. We determined that they possess two σ‐holes of differing electron deficiencies, with the more electropositive σ‐hole located opposite the dative I−C bond to the β‐dicarbonyl motif, and the lesser electropositive σ‐hole located opposite the iodoarene C−I bond. We also conducted the first systematic evaluation of carboxylic acids, phenols and thiophenols in the O/S‐alkylation reaction of iodonium ylides. While carboxylic acids and thiophenols were found to be generally viable, only phenols possessing electron‐withdrawing substituents were effective. This high‐yielding and highly chemoselective reaction is believed to involve halogen‐bond activation of heteroatoms, and nicely complements existing diazo‐based methods for alkylation of acidic functional groups.

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Section: Resultssupporting

confidence: 81%

σ‐Holes in Iodonium Ylides: Halogen‐Bond Activation of Carboxylic Acids, Phenols and Thiophenols May Enable Their X−H Insertion Reactions

Montgomery

Jameel

Cuzzucoli

et al. 2022

Chemistry A European J

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“…First, the reaction begins with the formation of phenyl‐Rh species through initial transmetallation of [Cp*RhCl 2 ] 2 and organoboron reagent [34] . Both H 2 O and CIY have the potential to facilitate this process, probably due to their abilities to form boron‐′ate′ species with organoboron compounds [35,13f] . Next, the coordination of iodonium ylide ( 10 ) to the metal center of the Ph−Rh species gives intermediate B , which further generates the Rh‐carbene intermediate C by loss of iodobenzene (carbenation process).…”

Section: Resultsmentioning

confidence: 99%

Catalytic and Base‐free Suzuki‐type α‐Arylation of Cyclic 1,3‐Dicarbonyls via a Cyclic Iodonium Ylide Strategy

Liang,

He,

Zhong

et al. 2024

Angew Chem Int Ed

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To date, it remains challenging to achieve a general and catalytic α‐arylation of cyclic 1,3‐dicarbonyls, particularly ubiquitous heteroaromatic ones. In most cases, the preparation of their medically significant arylated derivatives requires multistep synthetic sequences. Herein, we introduce a new, convenient strategy involving the conversion of cyclic 1,3‐dicarbonyls to cyclic iodonium ylides (CIYs), followed by rhodium‐catalyzed α‐arylation with arylboronic reagents via carbene coupling. This approach is mild, operationally simple, base‐free, biocompatible, and exhibits broad substrate scope (> 100 examples), especially with respect to various heteroaromatic 1,3‐dicarbonyls and ortho‐substituted or base‐sensitive arylboronic acids. Importantly, owing to the excellent compatibility with various arylboronic acids or boronate esters (ArBpin, ArBneop, or ArBF3K), this method allows the late‐stage installation of heterocyclic 1,3‐dicarbonyl motifs in highly complex settings. The utility of this transformation is further demonstrated through significantly simplifying the synthesis of several bioactive molecules and natural products.

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“…In 2020, Melen et al described an original access to dienolate-coordinated borinic acids by carboboration of iodonium ylides ( Scheme 58 ) [ 179 ]. They showed that mixing triarylboranes 171 with an equimolar amount of acyclic symmetrical or unsymmetrical iodonium ylides in toluene afforded compounds 173a–d in good yields.…”

Section: Cleavage Of One C-b Bondmentioning

confidence: 99%

Recent Advances in the Synthesis of Borinic Acid Derivatives

2023

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Borinic acids [R2B(OH)] and their chelate derivatives are a subclass of organoborane compounds used in cross-coupling reactions, catalysis, medicinal chemistry, polymer or optoelectronics materials. In this paper, we review the recent advances in the synthesis of diarylborinic acids and their four-coordinated analogs. The main strategies to build up borinic acids rely either on the addition of organometallic reagents to boranes (B(OR)3, BX3, aminoborane, arylboronic esters) or the reaction of triarylboranes with a ligand (diol, amino alcohol, etc.). After general practical considerations of borinic acids, an overview of the main synthetic methods, their scope and limitations is provided. We also discuss some mechanistic aspects.

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1,3-Carboboration of iodonium ylides

Abstract: Herein, we disclose the utilisation of iodonium ylides to access a range of boron dienolates.

Cited by 15 publications

References 25 publications

σ‐Holes in Iodonium Ylides: Halogen‐Bond Activation of Carboxylic Acids, Phenols and Thiophenols May Enable Their X−H Insertion Reactions

σ‐Holes in Iodonium Ylides: Halogen‐Bond Activation of Carboxylic Acids, Phenols and Thiophenols May Enable Their X−H Insertion Reactions

Catalytic and Base‐free Suzuki‐type α‐Arylation of Cyclic 1,3‐Dicarbonyls via a Cyclic Iodonium Ylide Strategy

Recent Advances in the Synthesis of Borinic Acid Derivatives

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