Nature, Год журнала: 2023, Номер 623(7985), С. 66 - 70
Опубликована: Сен. 20, 2023
Язык: Английский
Nature Communications, Год журнала: 2024, Номер 15(1)
Опубликована: Фев. 1, 2024
Macrolactones exhibit distinct conformational and configurational properties are widely found in natural products, medicines, agrochemicals. Up to now, the major effort for macrolactonization is directed toward identifying suitable carboxylic acid/alcohol coupling reagents address challenges associated with macrocyclization, wherein stereochemistry of products usually controlled by substrate's inherent chirality. It remains largely unexplored using catalysts govern both macrolactone formation stereochemical control. Here, we disclose a non-enzymatic organocatalytic approach construct macrolactones bearing chiral planes from achiral substrates. Our strategy utilizes N-heterocyclic carbene (NHC) as potent acylation catalyst that simultaneously mediates macrocyclization controls planar chirality during catalytic process. varying ring sizes sixteen twenty members obtained good-to-excellent yields enantiomeric ratios. study shall open new avenues accessing various stereogenic elements structures readily available small-molecule catalysts.
Язык: Английский
Процитировано
24
Chem, Год журнала: 2024, Номер 10(5), С. 1541 - 1552
Опубликована: Март 15, 2024
Язык: Английский
Процитировано
22
Nature Communications, Год журнала: 2024, Номер 15(1)
Опубликована: Янв. 12, 2024
Abstract We report an organocatalyst that combines a triazolium N-heterocyclic carbene (NHC) with squaramide as hydrogen-bonding donor (HBD), which can effectively catalyze the atroposelective ring-opening of biaryl lactams via unique amide C–N bond cleavage mode. The free species attacks carbonyl, forming axially chiral acyl-azolium intermediate. Various amines be accessed by this methodology up to 99% ee and yield. By using mercaptan catalyst turnover agent, resulting thioester synthon transformed into several interesting atropisomers. Both control experiments theoretical calculations reveal crucial role hybrid NHC-HBD skeleton, activates H-bonding brings it spatially close centre. This discovery illustrates potential chimera demonstrates complementary strategy for activation manipulation.
Язык: Английский
Процитировано
19
Coordination Chemistry Reviews, Год журнала: 2024, Номер 514, С. 215941 - 215941
Опубликована: Май 18, 2024
Язык: Английский
Процитировано
18
ACS Catalysis, Год журнала: 2022, Номер 12(5), С. 3111 - 3137
Опубликована: Фев. 21, 2022
Cobalt–N-heterocyclic carbene (NHC) complexes have emerged as an attractive class of 3d transition metal catalysts for a broad range chemical processes, including cross-coupling, hydrogenation, hydrofunctionalization, and cycloaddition reactions. Herein, we present comprehensive review catalytic methods utilizing cobalt–NHC with focus on the catalyst structure, role NHC ligand, properties system, mechanism, synthetic utility. The survey clearly suggests that recent emergence well-defined may tremendous utility in design application reactions using more abundant metals.
Язык: Английский
Процитировано
57
Chemical Communications, Год журнала: 2022, Номер 58(95), С. 13188 - 13197
Опубликована: Янв. 1, 2022
Improved stability and higher degree of synthetic tunability has allowed N-heterocyclic carbenes to supplant thiols as ligands for gold surface functionalization. This review article summarizes the basic science applications NHCs on gold.
Язык: Английский
Процитировано
57
Nature Communications, Год журнала: 2022, Номер 13(1)
Опубликована: Апрель 1, 2022
Abstract A catalytic method for the enantioselective and C4-selective functionalization of pyridine derivatives is yet to be developed. Herein, we report an efficient asymmetric β-pyridylations enals that involve N-heterocyclic carbene (NHC) catalysis with excellent control over enantioselectivity pyridyl C4-selectivity. The key strategy precise stereocontrol involves enhancing interactions between chiral NHC-bound homoenolate pyridinium salt in presence hexafluorobenzene, which effectively differentiates two faces radical. Room temperature sufficient this transformation, reaction efficiency further accelerated by photo-mediation. This methodology exhibits broad functional group tolerance enables facile access a diverse range enantioenriched β-pyridyl carbonyl compounds under mild metal-free conditions.
Язык: Английский
Процитировано
50
Journal of the American Chemical Society, Год журнала: 2022, Номер 144(34), С. 15431 - 15436
Опубликована: Авг. 17, 2022
Heterogeneous palladium catalysts modified by N-heterocyclic carbenes (NHCs) are shown to be highly effective toward the direct synthesis of hydrogen peroxide (H
Язык: Английский
Процитировано
46
Science China Chemistry, Год журнала: 2022, Номер 65(10), С. 1938 - 1944
Опубликована: Сен. 2, 2022
Язык: Английский
Процитировано
42
Chemistry - A European Journal, Год журнала: 2022, Номер 29(4)
Опубликована: Окт. 7, 2022
N-Heterocyclic carbene (NHC) catalysis is a by now consolidated organocatalytic platform for number of synthetic (asymmetric) transformations via diverse reaction modes/intermediates. In addition to the typical umpolung processes involving acyl anion/homoenolate equivalent species, implementation protocols under oxidative conditions greatly expands possibilities this methodology. Oxidative NHC-catalysis allows and oxygenative through specific manipulations Breslow-type species depending upon oxidant used (external or O
Язык: Английский
Процитировано
40