Single-carbon atom transfer reactions are lacking in organic synthesis, partly because of the absence atomic carbon sources under standard solution-phase conditions. We report here that N-heterocyclic carbenes can serve as donors through loss a 1,2-diimine moiety. This strategy is applicable to single-carbon α,β-unsaturated amides, which be converted into homologated γ-lactams formation four single bonds one center operation.

A unified and modular approach to the teleocidin B family of natural products is presented that proceeds in 11 steps features an array interesting strategies methods. Indolactam V, known biosynthetic precursor this family, was accessed through electrochemical amination, Cu-mediated aziridine opening, a remarkable base-induced macrolactamization. Guided by desire minimize concession steps, tactical combination C–H borylation Sigman–Heck transform enabled convergent, stereocontrolled synthesis...

Herein, we describe a new catalytic approach to accessing aromatic amines from an abundant feedstock, namely phenols. The most reliable method for converting phenols uses activating group, such as trifluoromethane sulfonyl group. However, this group is eliminated leaving during the amination process, resulting in significant waste. Our nickel-catalyzed decarboxylation reaction of aryl carbamates forms with carbon dioxide only byproduct. As proceeds absence free amines, range functionalities,...

A palladium-catalysed C2–H alkynylation of benzophospholes with alkynyl bromides has been developed to afford the corresponding phosphole-alkyne conjugations in good yields.

Although numerous transition‐metal catalyzed cross‐coupling reactions of alkenyl electrophiles with a sulfur(VI) leaving group, mainly sulfones, have been developed, most rely heavily on highly nucleophilic Grignard reagents, and the use organoboron reagents remains challenging. We report herein facile preparation following Pd‐catalyzed Suzuki‐Miyaura reaction sulfoximine, monoaza analog sulfone. The condensation alkyl sulfoximine aldehydes, developed in this study, makes sulfoximines more...

Although numerous transition‐metal catalyzed cross‐coupling reactions of alkenyl electrophiles with a sulfur(VI) leaving group, mainly sulfones, have been developed, most rely heavily on highly nucleophilic Grignard reagents, and the use organoboron reagents remains challenging. We report herein facile preparation following Pd‐catalyzed Suzuki‐Miyaura reaction sulfoximine, monoaza analog sulfone. The condensation alkyl sulfoximine aldehydes, developed in this study, makes sulfoximines more...

An unusual configurational stability of α-fluorovinyl radical holds significant potential to synthesize valuable monofluoroalkenes, bioisosteres amides, in a stereoselective fashion. However, the lack suitable precursor for this radical, generated manner, has hindered its application synthesis monofluoroalkenes. Herein, we report generation which reacts with disulfide form sulfides. This method hinges on two key reactions: condensation N-pivaloyl fluoromethyl sulfoximine an aldehyde...

A copper hydride (CuH)-catalyzed regio- and enantioselective hydroboration of 1-trifluoromethylseleno (SeCF3)-alkenes with H-Bpin has been developed. The hydrocupration an in situ generated CuH species is followed by a boration reaction to successfully construct SeCF3- Bpin-substituted chiral carbon center. key success the appropriate choice tBu-modified biphosphine ligands, which enables overwhelming high efficiency.

Abstract Concerted nucleophilic aromatic substitution (CS N Ar) has emerged as a powerful mechanistic manifold, in which can proceed one step without the need to form Meisenheimer intermediate. However, all of CS Ar reactions reported thus far require stoichiometric strong base or activating reagent, and no catalytic variants have yet been reported. Herein, we report an N‐heterocyclic carbene (NHC)‐catalyzed intramolecular cyclization acrylamides that contain 2‐fluorophenyl group on nitrogen...

We report on the N-heterocyclic carbene (NHC)-catalyzed Truce–Smiles rearrangement of aniline derivatives, in which an unactivated C(aryl)–N bond is cleaved, leading to formation a new C(aryl)–C bond. The key success this reaction utilization highly nucleophilic NHC, enables ylide intermediate that generated from α,β-unsaturated amide.

Abstract Despite recent progress in the catalytic transformation of inert phenol derivatives as alternatives to aryl halides and triflates, attempts at cross‐coupling with C−H bonds arenes have met limited success. Herein, we report rhodium‐catalyzed carbamates bearing a convertible directing group. The key success is use an situ generated rhodium bis(N‐heterocyclic carbene) species catalyst, which can promote activation C(sp 2 )−O bond carbamates.

A nickel-catalyzed three-component carboamination of the biphenylene C–C σ-bond has been developed. Arylboronates and hydroxylamine derivatives work as carbon nucleophiles nitrogen electrophiles, respectively, corresponding difunctionalized ring-opening products are obtained in good yields. The arylboronate nucleophile can be replaced with B2pin2 (boron nucleophile) H–Si(OMe)3 (hydride nucleophile), thus allowing for aminoboration hydroamination under similar nickel catalysis.

The rhodium-catalyzed alkynylation of aryl carbamates with propargyl alcohols is described. This methodology can provide acetylenes from via C–O bond activation. use as alkynylating agents allows the a variety functional groups that are incompatible organometallic nucleophiles. reaction also serves to broaden utility carbamate moiety convertible ortho directing group.

Abstract This Award Account reports our recent studies concerning the catalytic transformations that involve a non-classical mode of molecular activation by tertiary phosphines and N-heterocyclic carbenes (NHCs). Regarding organophosphine catalysis, we successfully designed reactions based on P(III)/P(V) redox couple. A protocol for generating pentacoordinate P(V) species was devised reaction phosphines, acyl fluorides alkynoates. The ability thus generated fluorophosphoranes to participate...

Despite the widespread use of carbamates as a directing group in C–H bond-functionalization reactions, reductive removal this is not straightforward. Currently available methods are limited to nickel-catalyzed reactions using i PrMgX or hydrosilane reductant, leaving functional compatibility issue be solved. Herein, we report rhodium-catalyzed cleavage aryl iPrOH milder reductant.

Despite recent progress in the catalytic transformation of inert phenol derivatives as alternatives to aryl halides and triflates, attempts at cross-coupling with C−H bonds arenes have met limited success. Herein, we report rhodium-catalyzed carbamates bearing a convertible directing group. The key success is use an situ generated rhodium bis(N-heterocyclic carbene) species catalyst, which can promote activation C(sp2)−O bond carbamates.

A novel approach to the direct construction of tricyclic nitrogen heterocycles based on gold-catalyzed cascade cyclization aminoallenynes is described. The expected biscyclization reaction hydroxyisobutyryl-protected was efficiently promoted by a catalytic amount BrettPhosAuNTf2 in presence iPrOH produce 1,2-dihydrobenzo[cd]indole derivatives good yields. When combined with Friedel-Crafts acylation or palladium-catalyzed N-arylation, resulting products were converted into nitrogen-containing...

Auxiliaries are crucial for achieving high selectivity in synthesizing complex molecules, particularly pharmaceuticals and natural products. However, their application has primarily been limited to specific selectivity, such as the stereoselectivity of asymmetric reactions regioselectivity C–H functionalization. Our hypothesis was that expanding this concept other requiring could enable synthesis otherwise challenging molecules. Here, we introduce a conceptually new auxiliary, aptly termed...

Abstract We report here that the reactivity order of leaving group is F > Cl ≥ Br I in N-heterocyclic carbene-catalyzed CSNAr reactions aryl halides bearing an α,β-unsaturated amide. Based on a qualitative Marcus analysis, nature transition state this catalytic primarily determined by potential energy Meisenheimer complex, even though it not involved as discrete intermediate reaction pathway.

Abstract Concerted nucleophilic aromatic substitution (CS N Ar) has emerged as a powerful mechanistic manifold, in which can proceed one step without the need to form Meisenheimer intermediate. However, all of CS Ar reactions reported thus far require stoichiometric strong base or activating reagent, and no catalytic variants have yet been reported. Herein, we report an N‐heterocyclic carbene (NHC)‐catalyzed intramolecular cyclization acrylamides that contain 2‐fluorophenyl group on nitrogen...

The asymmetric oxidation of a sulfur-containing nine-membered heterocycle was achieved for the late-stage introduction chirality to substituents π-electron systems. sulfur atom considerably influenced phase-transition behaviour and crystallinity resulting

Although numerous transition-metal catalyzed cross-coupling reactions of alkenyl electrophiles with a sulfur(VI) leaving group, mainly sulfones, have been developed, most rely heavily on highly nucleophilic Grignard reagents, and the use organoboron reagents remains challenging. We report herein facile preparation following Pd-catalyzed Suzuki-Miyaura reaction sulfoximine, monoaza analog sulfone. The condensation alkyl sulfoximine aldehydes, developed in this study, makes sulfoximines more...

A Bi(OTf) 3 -assisted, visible-light-promoted dehydrogenative cyclization of 2,3-diarylbenzophospholes proceeds to form the corresponding highly condensed dibenzophospholes interest in material chemistry.

The discovery of small organic compounds for inducing stem cell differentiation is a time- and resource-intensive process. While data science could, in principle, facilitate the these compounds, novel approaches are required due to difficulty acquiring training from large numbers example compounds. In this paper, we demonstrate design new compound cardiomyocyte using simple regression models trained with set containing only 80 examples. We introduce decorated shape descriptors, an...