C−Boron Enolates Enable Palladium Catalyzed Carboboration of Internal 1,3‐Enynes

Wang, Ziyong; Wu, Jason; Lamine, Walid; Li, Bo; Sotiropoulos, Jean‐Marc; Chrostowska, Anna; Miqueu, Karinne; Liu, Shih‐Yuan

doi:10.1002/anie.202108534

Cited by 26 publications

(16 citation statements)

References 90 publications

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“…We are pleased to determine that heteroaryl derived enynes (furan: entry 8 k, and thiophene: entry 8 l) are excellent substrates for the carboboration reaction. We have obtained the X-ray crystal structure of 8 e, [25] thus unambiguously establishing the connectivity and the diastereoselectivity of the reaction product. Notably, the [a,b] [a] See SI for detailed procedure.…”

Section: Angewandte Chemiementioning

confidence: 78%

C−Boron Enolates Enable Palladium Catalyzed Carboboration of Internal 1,3‐Enynes

Wang

Lamine

et al. 2021

Angewandte Chemie

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A new family of carbon-bound boron enolates, generated by a kinetically controlled halogen exchange between chlorocatecholborane and silylketene acetals, is described. These CÀboron enolates are demonstrated to activate 1,3-enyne substrates in the presence of a Pd 0 /Senphos ligand complex, resulting in the first examples of a carboboration reaction of an alkyne with enolate-equivalent nucleophiles. Highly substituted dienyl boron building blocks are produced in excellent site-, regio-, and diastereoselectivity by the described catalytic cis-carboboration reaction.Alkenyl boronates are versatile building blocks in synthetic chemistry. [1] The ability of organoboron compounds to engage in Suzuki-Miyaura cross couplings [2] and to transform into various derivatives [3] have made alkenyl boronates highly appealing in organic synthesis. In this context, numerous approaches [4] have been developed to synthesize di- [5] and tri- [6] substituted alkenyl boronates. The synthesis of tetrasubstituted alkenyl [7] boronates on the other hand, particularly in regioselective and stereoselective fashion, has been more challenging. [8] Pioneering work by Suginome et al. (Scheme 1 a) established the nickel-or palladium catalyzed intramolecular boryl migration approach using alkyne substrates tethered with boryl moiety. [9] Similarly, nickel and palladium catalyzed intermolecular carboboration of alkynes with various carbon sources (Scheme 1 b) was reported. [10] More recently, copper-catalyzed three-component coupling of an alkyne, B 2 pin 2 , and an electrophile (Scheme 1 c) has received attention. [11] Despite these advances, carboboration reactions are still relatively limited in substrate scope and generality. In particular, stereoselective carboborations to produce tetrasubstituted alkenes often face regio-and dia-stereoselectivity issues for internal unsymmetrical alkynes. [11a-e] We recently reported the trans-hydroboration and trans-cyanoboration of 1,3-enynes catalyzed by a 1,4-azaborine biaryl phosphine (Senphos)-Pd complex. [12] An unusual outer-sphere oxidative addition mechanism [13] (a cooperative activation of the 1,3-Scheme 1. Regio-and stereoselective synthesis of tetrasubstituted alkenyl boronates.

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Section: Angewandte Chemiementioning

confidence: 78%

C−Boron Enolates Enable Palladium Catalyzed Carboboration of Internal 1,3‐Enynes

Wang

Lamine

et al. 2021

Angewandte Chemie

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“…Recently, the anti ‐cyanoboration of enynes was developed by Liu group [70] using a 1,4‐azaborine phosphine‐based ligand (Senphos) to enhance the anti ‐stereoselectivity (Scheme 26a). The same group have recently developed the selective carboboration of 1,3‐enynes with a C‐boron enolate [71] . A cooperative activation of the enyne by Pd‐catalyst and boron reagent led to regio‐ and diastereoselective tetrasubstituted alkenyl boronates in a syn ‐carboboration (Scheme 26b).…”

Section: Carboboration Of Alkynesmentioning

confidence: 99%

Synthesis of Tri‐ and Tetrasubstituted Alkenyl Boronates from Alkynes

et al. 2022

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The synthesis of organoboron compounds have attracted the attention of the synthetic community. In particular, molecules with C(sp2)‐B bonds enable the transformation to new C−C or C‐heteroatom bonds by well‐established methodologies. Alkenyl boronates have the possibility for further conversion of the boron moiety or functionalization of the double bond. This review gives an overview on the recent methodologies for the selective preparation of the challenging highly substituted alkenyl boronates from alkynes.

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“…In addition, the recently reported BN-perylene ( IV , R = methyl) possesses a wider HOMO–LUMO gap than all carbon perylene . The field of BN-PAHs chemistry has already undergone considerable growth in the past two decades, and the concept of BN/CC isosterism has help advance contemporary research in the areas of catalysis, biomedical, and material , science.…”

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confidence: 99%

Synthesis, Characterization, and Properties of BN-Fluoranthenes

Jin

Jiang

et al. 2022

Org. Lett.

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Boron/nitrogen-doped fluoranthenes, a new class of BN-doped cyclopenta-fused polycyclic aromatic hydrocarbons, were synthesized via pyrrolic-type nitrogen directed C−H borylation. Regioselective bromination of BN-fluoranthene (3a) gave mono-and dibrominated BN-fluoranthenes. The halogenated BN-fluoranthene (3b) can undergo various of further crosscoupling reactions to deliver a series of BN-fluoranthenes. Moreover, incorporating BN unit in to fluoranthene resulted in a wider HOMO−LUMO energy gaps. The aromaticities of the BN-fluoranthene (3a) were quantified by experimental and computational studies.

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C−Boron Enolates Enable Palladium Catalyzed Carboboration of Internal 1,3‐Enynes

Cited by 26 publications

References 90 publications

C−Boron Enolates Enable Palladium Catalyzed Carboboration of Internal 1,3‐Enynes

C−Boron Enolates Enable Palladium Catalyzed Carboboration of Internal 1,3‐Enynes

Synthesis of Tri‐ and Tetrasubstituted Alkenyl Boronates from Alkynes

Synthesis, Characterization, and Properties of BN-Fluoranthenes

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