Organic Letters, Journal Year: 2024, Volume and Issue: unknown
Published: Dec. 4, 2024
Herein we successfully utilize various directing groups to achieve a ligand-enabled nickel-catalyzed 1,2-borylalkylation of unactivated alkenes. A β-amino alcohol was employed as the ligand for non-asymmetric alkenes, while bulky chiral diamine used asymmetric allyl amides.
Language: Английский
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(24), P. 16892 - 16901
Published: June 6, 2024
The development of a catalytic method for stereogenic carbon center formation holds immense significance in organic synthesis. Transition-metal-catalyzed cross-coupling reaction has been regarded as straightforward and efficient tool stereoselectively forging C–C bond. Nevertheless, the creation acyclic all-carbon quaternary-containing vicinal stereocenters remains notoriously challenging within domain chemistry despite their prominence various bioactive small molecules. Herein, we describe palladium-catalyzed asymmetric multicomponent trisubstituted alkene with aryl diazonium salts arylboronic acids to realize tertiary-quaternary centers high regio-, distereo-, enantioselectivity. Specifically, precise manipulation stereoconfiguration alkenes enables divergent stereoselective reaction, thus allowing facile construction all four enantiomers. Harnessing ligand-swap strategy involving chiral bisoxazoline an achiral fumarate individually accelerates enantioselective migratory insertion reductive elimination step process, supported by density functional theory (DFT) calculations, obviating requirement neighboring directing group internal olefin skeleton.
Language: Английский
Citations
10
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18866 - 18872
Published: July 5, 2024
C-Glycosides are important structures that common to natural products and pharmaceutical agents. Established methods for their synthesis involve the reaction of an activated anomeric carbon. In this study, we report a conceptually new approach involves stereoselective Ni-catalyzed carboboration glycals. these reactions, not only is C–C bond formed at carbon, but synthetically useful C–B also installed. Upon oxidation, differentially protected C-glycosides be formed. addition, stereospecific manipulation leads diverse C-glycosides. Finally, application method in established C-glycosides, such as C-glycosyl amino acids, well strategy make all possible diastereomers C1 C2.
Language: Английский
Citations
10
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(25), P. 17140 - 17149
Published: June 12, 2024
Enantioselective three-component difunctionalization of alkenes with boron reagents represents an attractive strategy for assembling three-dimensional chiral organoboron compounds. However, regio- and enantiocontrol comprise the pivot challenges in these transformations, which predominantly require use activated conjugated alkenes. Herein, by utilizing various carbonyl directing groups, including amides, sulfinamides, ketones, esters, we succeed realizing a nickel-catalyzed 1,2-borylalkynylation unactivated to enable simultaneous incorporation entity sp-fragment across double bond. The products contain boryl, alkynyl, functional groups orthogonal synthetic reactivities, offering three handles further derivatization access valuable intermediates. utility this ligand-enabled asymmetric protocol has been highlighted through late-stage decoration drug-relevant molecules.
Language: Английский
Citations
8
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(32), P. 22413 - 22423
Published: Aug. 3, 2024
Stereochemically pure saccharides have indispensable roles in fields ranging from medicinal chemistry to materials science and organic synthesis. However, the development of a simple, stereoselective, efficient glycosylation protocol access α- β-C-glycosides (particularly 2-deoxy entities) remains persistent challenge. Existing studies primarily focused on C1 modification carbohydrates transformation glycosyl radical precursors. Here, we innovate by harnessing situ generated glycosyl-Ni species achieve one-pot borylation cascade manner, which is enabled an earth-abundant nickel-catalyzed carboboration readily accessible glycals without any ligand. This work reveals potential for modular multifunctional platform facilitate simultaneous introduction C-C C-B bonds at stereogenic center saccharides, largely unexploited research area. Preliminary experimental computational indicate that endocyclic O C3 group play important stereoseclectively forging glycosidic bonds. As result, diverse range C-R (R = alkyl, aryl, alkenyl) 2-deoxygenated glycosides bearing modifiable boron groups could be rapidly made with excellent stereocontrol exhibit remarkable functional tolerance. The synthetic underscored late-stage natural products commercial drugs as well facile preparation various rare sugars, bioactive conjugates, key intermediates prorocentin, phomonol, aspergillide A.
Language: Английский
Citations
5
Organic Letters, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 10, 2025
A three-component cascade boronation–dearomatization reaction of alkenes, a diboron compound, and pyridinium salt is diclosed, affording chiral boron-containing 1,4-dihyropyridines in high yields (≤98%) diastereoselectivity (≤10:1 dr), along with excellent enantioselectivity (typically >99% ee). The catalytic system performs efficiently at low catalyst loadings (1 mol %) was tested >50 examples, including some biologically active molecules.
Language: Английский
Citations
0
Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 111050 - 111050
Published: March 1, 2025
Language: Английский
Citations
0
Organic Letters, Journal Year: 2025, Volume and Issue: unknown
Published: May 7, 2025
A photoinduced radical arylboration of unactivated alkenes with B2pin2 and aryl nitriles was developed, providing a mild efficient approach to access useful β-aryl boronates in the absence transition-metal catalyst. This reaction undergoes boron addition alkene subsequent radical-radical coupling process. showcases good functional group compatibility provides promising complementary strategy chemistry traditional transition-metal-catalyzed coupling.
Language: Английский
Citations
0
Organic Letters, Journal Year: 2025, Volume and Issue: unknown
Published: June 5, 2025
Internal allenes are challenging substrates in copper-catalyzed borylative difunctionalization. When internal featuring a methylidenecyclobutane motif were employed, hydrofunctionalization reaction using diborons and ketones as partners the presence of chiral monophosphorus ligand was developed, affording series unsaturated tertiary alcohols preserving high regio- stereoselectivities. Control experiments suggest that involves boronation-deboronation process, plausible mechanism has been proposed.
Language: Английский
Citations
0
Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(20), P. 2485 - 2498
Published: June 21, 2024
Comprehensive Summary The construction of acyclic quaternary carbon stereocenters, which are ubiquitous in many bioactive compounds, pharmaceuticals and natural products, has been a long persuit synthetic organic chemistry. Among numerous methods, enantioselective nickel‐catalysis attracted incremental attention recent years. This review summarizes the development asymmetric strategies, research progress, mechanistic investigations for generation stereocenters via nickel catalysis. Key Scientists In 2006, Zhou group RajanBabu realized nickel‐catalyzed hydrovinylation α‐substituted styrenes ethylene to construct (QCSs) by using spiro‐ binaphthyl phosphoramidite ligands, respectively. 2016, Watson developed Suzuki‐Miyaura arylation generate QCSs chirality transfer reaction. 2017, Feng Fu conjugated/Michael additions build QCSs, 2020, Fang made first success hydrocyanation alkenes allenes. 2021, Gregory C. co‐workers disclosed α‐functionalization carbonyl compounds that could form QCSs. At same time, Shi constructed chiral functionalization alkenes. 2023, Kleij applied new strategy Ni‐catalyzed regio‐ homoallylic coupling year, Tao demonstrated novel is dinickel‐catalyzed α‐alkylation with alkyl iodides.
Language: Английский
Citations
2
Elsevier eBooks, Journal Year: 2024, Volume and Issue: unknown
Published: Jan. 1, 2024
Language: Английский
Citations
0