Boron‐Copper 1,3‐Rearrangement: the New Concept Behind the Boryl Migration from C(sp²) in Alkenyl Boranes to C(sp³)

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(30)

Опубликована: Май 11, 2023

Regioselective borylcupration of borylated skipped (Z)-dienes generates diborylated alkylcopper species that are involved in an intramolecular stereospecific B/Cu 1,3-rearrangement by migration Bpin moiety from C(sp2 ) to C(sp3 ). DFT mechanistic studies showed boryl occurs through the formation 4-membered boracycle intermediate with a moderate free-energy barrier. Moreover, use KOMe forms stable Lewis base adducts moieties blocks reaction. Subsequently 1,3-boron shift, situ electrophilic trapping allows selective C-H, C-C and C-X bonds, followed cross coupling giving access cyclic functionalized alkylidenecyclohexanes or alkylidenecyclobutanes.

Язык: Английский

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Site‐Selective (Z)‐α‐Borylalkenyl Copper Systems for Nucleophilic Stereodefined Allylic Coupling

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(37)

Опубликована: Июль 20, 2022

1,1-Diborylalkenes can be transformed into (Z)-skipped dienes through CuI -phosphine catalyzed allylic coupling reactions. The energetically preferred formation of (Z)-α-borylalkenyl copper (I) species and the subsequent nucleophilic attack, explains stereoselective substitution with allyl bromides. eventual treatment NaOt Bu promotes cyclization/aromatization patterns via enyne intermediates.

Язык: Английский

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Ru(0)-Catalysed synthesis of borylated polyene building blocks by cross-dimerisation toward cross-coupling

Chemical Communications, Год журнала: 2024, Номер 60(60), С. 7672 - 7686

Опубликована: Янв. 1, 2024

Conjugated and non-conjugated polyenes are important substructures often found in biologically active compounds natural products. Their preparation needs multiple steps or iterative reactions as a result, they have poor step economies. In this feature article, we show new methodology to prepare these by combinations of cross-dimerisation giving borylated subsequent cross-coupling reactions. This divergent reaction strategy allows for the opportunity access many bioactive products well some electronic materials.

Язык: Английский

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Stereoselective C−B and C−H Bonds Functionalization of PolyBorylated Alkenes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(45)

Опубликована: Июль 9, 2024

Abstract Alkenes are fundamental functional groups which feature in various materials and bioactive molecules; however, efficient divergent strategies for their stereodefined synthesis difficult. In this regard, numerous synthetic methodologies have been developed to construct carbon–carbon bonds with regio‐ stereoselectivity, enabling the predictable of alkenes. fact, an appealing alternative approach accessing challenging alkene molecular frameworks could involve sequential selective activation cross‐coupling strong instead conventional C−C bond formation. study, we introduce a series programmed site‐ stereoselective that capitalizes on versatile reactivity readily accessible polymetalloid alkenes (i.e. polyborylated alkenes), through tandem reaction, is catalyzed by organometallic Rh‐complex produce complex scaffolds. By merging C−B remote C−H functionalization, achieve situ generation polyfunctional C(sp 2 )‐nucleophilic intermediates. These species can be further modified coupling reactions C‐based electrophiles, formation )−C(sp 3 ) even more architectures using available starting polyborylated‐alkenes. Mechanistic computational studies provide insight into origins stereoselectivities via 1,4‐Rh migration process.

Язык: Английский

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Stereoselective Control of the Cu Activation of β,β-Diboryl Acrylates for Allylic Coupling Protocols with Concomitant Lactonization

Organic Letters, Год журнала: 2023, Номер 26(14), С. 2821 - 2826

Опубликована: Дек. 15, 2023

The key to a successful C–B activation is discriminate between two geminal boryl moieties that are exposed the same reaction conditions. Here we describe stereoselective of β,β-diboryl acrylates forming exclusively (Z)-α-borylalkenyl copper(I) intermediate, for subsequent allylic alkylation reactions. new borylated (Z)-skipped dienoates followed feasible iodo-lactonization sequence preparation lactone cores, which can be used in drug discovery.

Язык: Английский

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Boron‐Copper 1,3‐Rearrangement: the New Concept Behind the Boryl Migration from C(sp²) in Alkenyl Boranes to C(sp³)

Angewandte Chemie, Год журнала: 2023, Номер 135(30)

Опубликована: Май 11, 2023

Abstract Regioselective borylcupration of borylated skipped ( Z )‐dienes generates diborylated alkylcopper species that are involved in an intramolecular stereospecific B/Cu 1,3‐rearrangement by migration Bpin moiety from C(sp 2 ) to 3 ). DFT mechanistic studies showed boryl occurs through the formation 4‐membered boracycle intermediate with a moderate free‐energy barrier. Moreover, use KOMe forms stable Lewis base adducts moieties blocks reaction. Subsequently 1,3‐boron shift, situ electrophilic trapping allows selective C−H, C−C and C−X bonds, followed cross coupling giving access cyclic functionalized alkylidenecyclohexanes or alkylidenecyclobutanes.

Язык: Английский

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Stereoselective C−B and C−H Bonds Functionalization of PolyBorylated Alkenes

Angewandte Chemie, Год журнала: 2024, Номер 136(45)

Опубликована: Июль 9, 2024

Abstract Alkenes are fundamental functional groups which feature in various materials and bioactive molecules; however, efficient divergent strategies for their stereodefined synthesis difficult. In this regard, numerous synthetic methodologies have been developed to construct carbon–carbon bonds with regio‐ stereoselectivity, enabling the predictable of alkenes. fact, an appealing alternative approach accessing challenging alkene molecular frameworks could involve sequential selective activation cross‐coupling strong instead conventional C−C bond formation. study, we introduce a series programmed site‐ stereoselective that capitalizes on versatile reactivity readily accessible polymetalloid alkenes (i.e. polyborylated alkenes), through tandem reaction, is catalyzed by organometallic Rh‐complex produce complex scaffolds. By merging C−B remote C−H functionalization, achieve situ generation polyfunctional C(sp 2 )‐nucleophilic intermediates. These species can be further modified coupling reactions C‐based electrophiles, formation )−C(sp 3 ) even more architectures using available starting polyborylated‐alkenes. Mechanistic computational studies provide insight into origins stereoselectivities via 1,4‐Rh migration process.

Язык: Английский

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Coupling Reactions Between sp3 and sp2 Carbon Centers

Elsevier eBooks, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Язык: Английский

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