Elsevier eBooks, Год журнала: 2024, Номер unknown
Опубликована: Янв. 1, 2024
Язык: Английский
Elsevier eBooks, Год журнала: 2024, Номер unknown
Опубликована: Янв. 1, 2024
Язык: Английский
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
Процитировано
10Angewandte 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
Процитировано
8Chemical 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
Процитировано
1Angewandte 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
Процитировано
1Organic 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
Процитировано
3Angewandte 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
Процитировано
2Angewandte 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
Процитировано
0Elsevier eBooks, Год журнала: 2024, Номер unknown
Опубликована: Янв. 1, 2024
Язык: Английский
Процитировано
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