The influential IPr: 25 years after its discovery

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

25 Years after the discovery of most influential NHC ligand, we revisit and highlight studies involving IPr that have shaped field NHC-transition metal catalysis.

Язык: Английский

---

Silver(I)-Catalyzed Stereochemical Isomerization of Cyclopropanols

Organometallics, Год журнала: 2025, Номер unknown

Опубликована: Янв. 16, 2025

Isomerization of cyclopropane-containing molecules offers a direct pathway to access all their diastereoisomers. Current catalytic methods, however, are largely confined isomerization carbonyl- and vinyl-substituted cyclopropanes. We report cyclopropanols, which converts readily accessible cis-1,2-disubstituted cyclopropanols into more stable, yet often less accessible, trans-isomers. This enables straightforward both diastereoisomers these small-ring molecules. Mechanistic studies indicate the reactivity silver homoenolates.

Язык: Английский

---

Photocatalyzed Epimerization of Quaternary Stereocenters

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 19, 2025

Quaternary stereocenters play a crucial role in shaping both the molecular topology of small molecules and outcome stereoselective transformations. While considerable progress has been achieved constructing highly substituted carbon centers with varied substitution patterns, synthesis quaternary remains significant challenge. Here we report protocol for precise manipulation through epimerization. The critical design element our ketone α-epimerization process was developing photoactive imine, which circumvents numerous deleterious pathways carbonyl photochemistry. Excitation this imine visible light presence photocatalyst enables reversible C–C bond cleavage reformation to vary stereochemistry center. This approach allows us override intrinsic stereochemical outcomes construction, therefore providing novel tactics retrosynthetic planning. broad utility demonstrated by topological alteration various classes carbocyclic scaffolds bearing diverse functional groups.

Язык: Английский

---

Nickel catalyzed C-N coupling of haloarenes with B2N4 reagents

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Апрель 3, 2025

Язык: Английский

---

Diastereoselective Synthesis of Boryl-Substituted Vinylcyclopropanes via Deborylative Cyclization of Geminal Diboron Compounds

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 14, 2025

Herein we report a diastereoselective synthesis of boryl-substituted vinylcyclopropanes, class highly valuable synthetic building blocks, via deborylative cyclization geminal diboron compounds. The method exhibits broad functional group tolerance and accommodates diverse alkyl aryl α-substituents. diastereoselectivity is primarily governed by the α-substituent (alkyl vs aryl), while olefin geometry in side chain has secondary influence. Mechanistic studies indicated distinct pathways: concerted process for substrates carbanion intermediate derivatives. Synthetic utility products was also demonstrated.

Язык: Английский

---

Catalytic Metalloradical System for Radical 1,6-C(sp³)–H Amination with Concurrent Control of Site-, Chemo-, and Enantio-selectivity

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 22, 2025

A catalytic radical process has been developed via metalloradical catalysis (MRC) for 1,6-C(sp3)-H amination with concurrent control of site-, chemo-, and enantioselectivity. Supported by an optimal D2-symmetric chiral amidoporphyrin ligand, the Co(II)-based system effectively catalyzes chemoselective propargylic, allylic, benzylic C-H bonds at 1,6- over 1,5-positions alkoxysulfonyl azides, achieving high This Co(II)-catalyzed process, which operates room temperature, is applicable to a broad range azides tolerance functional groups, enabling efficient construction six-membered sulfamidates in yields excellent enantioselectivities. Comprehensive experimental investigations, complemented computational studies, elucidate stepwise mechanism underlying this transformation. The resulting cyclic from enantioselective can undergo stereospecific ring-opening reactions various nucleophiles, affording γ-functionalized α-chiral amines while retaining original enantiopurity. Since are readily synthesized widely available alcohols through nucleophilic azide transfer, union ionic processes constitutes versatile 1,3-difunctionalization alcohols.

Язык: Английский

---

Electrochemical 1,5-chlorosulfonylation and 1,5-hydrosulfonylation of vinylcyclopropanes

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(19), С. 5564 - 5572

Опубликована: Янв. 1, 2024

This study reports the electrochemical reaction of vinylcyclopropanes with sulfonyl chlorides, resulting in 1,5-hydrosulfonylation and 1,5-chlorosulfonylation.

Язык: Английский

---

Alkene Cyclopropanation with gem-Dichloroalkanes Catalyzed by (PNN)Co Complexes: Scope and Mechanism

ACS Catalysis, Год журнала: 2024, Номер 14(17), С. 12846 - 12856

Опубликована: Авг. 12, 2024

Highly regioselective and diastereoselective cis-arylcyclopropanation (ACP) trans-vinylcyclopropanation (VCP) of 1-alkenes with gem-dichloroalkanes are described. By employing stable readily available donor carbene precursors zinc powder as the additive, cobalt dichloride complex (tBuPNN)CoCl2 a phosphinobipyridine (PNN) pincer tBu substituents on phosphorus atom catalyzes mild efficient cyclopropanation high functional-group compatibility wide substrate scope, furnishing diastereoselectivity in case trans-VCP that remains underdeveloped. The synthetic potential was demonstrated by late-stage modification bioactive molecules. Stoichiometric experiments cyclic voltammetry provide insights into reaction mechanism identify key factors to achieve this reaction; particular importance is relatively slow reduction gem-dichloroalkane formal CoI species (tBuPNN)CoCl keep free alkyl radical at low concentration, elucidated relationship between catalytic activity potentials four (tBuPNN)Co complexes various electronic properties.

Язык: Английский

---

Rh-Catalyzed trans-Divinylcyclopropane Rearrangement: An Approach to 1,5-Disubstituted 1,4-Cycloheptadienes

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Дек. 19, 2024

Under mild conditions and without the need of inert gas protection, a Rh-catalyzed rearrangement

Язык: Английский

---