Chromium-catalyzed enantioselective Nozaki-Hiyama-Kishi (NHK) reaction represents one of the most powerful approaches for formation chiral carbon-heteroatom bond. However, construction sterically encumbered tetrasubstituted stereocenter through NHK still posts a significant challenge. Herein, we disclose cobalt-catalyzed aza-NHK ketimine with alkenyl halide to provide convenient synthetic approach manufacture enantioenriched α-vinylic amino acid. This protocol exhibits excellent functional...

Herein, we report a nickel-catalyzed reductive cross-coupling reaction of easily accessible 3-butenyl carbamoyl chloride with primary alkyl iodide to access the chiral α-alkylated pyrrolidinone broad substrate scope and high enantiomeric excess. The current art synthesis still remains challenging on enantioselective α-monoalkylation pyrrolidinones. newly designed 8-quinoline imidazoline ligand (Quinim) is crucial for maintaining reactivity enantioselectivity ensure cyclization...

The construction of multi-stereocenters by a transition metal-catalyzed cross-coupling reaction is major challenge. catalytic desymmetric functionalization unactivated alkenes remains largely unexplored. Herein, we disclose -a dicarbofunctionalization 1,6-dienes via nickel-catalyzed reductive reaction. leverage the underdeveloped chiral 8-Quinox enables Ni-catalyzed carbamoylalkylation both mono- and disubstituted to form pyrrolidinone bearing two nonadjacent stereogenic centers in high...

We describe a nickel-catalyzed carbonylative cross-coupling of unactivated secondary alkyl electrophiles with the organozinc reagent at atmospheric CO gas, thus allowing expedient construction unsymmetric dialkyl ketones broad functional group tolerance. The leverage newly developed

β-Tertiary amino acid derivatives constitute one of the most frequently occurring units in natural products and bioactive molecules. However, efficient asymmetric synthesis this motif still remains a significant challenge. Herein, we disclose cobalt-catalyzed enantioselective reductive addition reaction ketimine using α-chloro carbonyl compound as radical precursor, providing expedient access to diverse array enantioenriched β-quaternary analogues. This protocol exhibits outstanding...

Herein, we reported a Ni-catalyzed carbonylation of cyclopropanol with benzyl bromide to afford multisubstituted cyclopentenone under 1 atm CO. The reaction proceeds through cascade bromides, followed by generation nickel homoenolate from cyclopropanols via β-C elimination 1,4-diketones, which undergoes intramolecular Aldol condensation furnish highly substituted derivatives in moderate good yields. exhibits high functional group tolerance broad substrate scope.

Herein, we leverage the Ni-catalyzed enantioselective reductive dicarbofunctionalization of internal alkenes with alkyl iodides to enable synthesis chiral pyrrolidinones bearing vicinal stereogenic centers. The application newly developed

Abstract Nitrogen-based heterocycles have aroused widespread interest due to their reoccurrence in many pharmaceuticals. Amongst these motifs, the enantioenriched lactams are ubiquitous scaffolds found myriad biologically active natural products and drugs. Recently, transition metal-catalyzed asymmetric carbamoylation has been widely employed as a straightforward arsenal for chiral lactam architecture synthesis, including β-lactam γ-lactam. However, despite extensive efforts, there still...

Comprehensive Summary Transition metal‐catalyzed difunctionalization of tethered alkene has emerged as a prevailing tool for the expedient construction synthetically valuable cyclic compounds. However, most efforts have been devoted to reaction styrene‐type substrates due their rigid scaffold and high reactivity. With respect nonaromatic olefin, especially mono‐substituted alkene, still remains largely underdeveloped. Herein, we disclose nickel/Quinim complex TBADT‐cocatalyzed asymmetric...

This review highlights the recent advancements of carbamoyl chlorides in transition metal-catalyzed reactions to access various amide-containing molecules and heterocycles.

Open AccessCCS ChemistryCOMMUNICATIONS19 Aug 2022Enantioselective Synthesis of α-Alkenylated γ-Lactam Enabled by Ni-Catalyzed 1,4-Arylcarbamoylation 1,3-Dienes Feng He, Liting Hou, Xianqing Wu, Haojie Ding, Jingping Qu and Yifeng Chen He Key Laboratory for Advanced Materials Joint International Research Precision Chemistry Molecular Engineering, Feringa Nobel Prize Scientist Center, Frontiers Science Center Materiobiology Dynamic Chemistry, School East China University Technology, Shanghai...

A nickel-catalyzed alkoxycarbonylation of aromatic iodides with alcohols under atmospheric pressure carbon monoxide is presented here. This operationally simple protocol allows the facile synthesis (hetero)aromatic esters, exhibiting broad substrate scope excellent functional group tolerance. Various primary and secondary aliphatic as well phenols are suitable for this transformation.

We report herein a miscellaneous oxindole synthesis bearing an all-carbon quaternary center, enabled by Pd-catalyzed intramolecular cyclization followed multiple intermolecular Heck reactions of both easily accessible alkene-tethered carbamoyl chlorides and olefins. This protocol obviates the use prefunctionalized olefinic reagents, exhibits excellent functional group tolerance, features fascinating reactive versatility.

Reported herein is a palladium/copper cooperative-catalyzed dicarbofunctionalization of alkene-tethered carbamoyl chlorides with 1,1-diborylmethane. This cyclization/deborylation cascade strategy allows for the expedient formation versatile borylated 3,3-disubstituted oxindole skeleton, allowing further functionalization via derivatization carbon-boron bond.

Transition metal-catalyzed carbonylative reaction with CO gas are among the central task in organic synthesis, enabling construction of highly valuable carbonyl compound. Here, we show an earth-abundant nickel-catalyzed three-component tandem acylzincation/cyclization sequence allene and alkylzinc reagent 1 atm under mild conditions. This protocol is featured by broad functional group tolerance high selectivity, providing a rapid convenient synthetic method for diverse fully substituted...

A nickel-catalyzed three-component carbonylative cross-coupling reaction of allylic alcohols and organoalanes with CO at atmospheric pressure is reported, enabling the expedient formation β,γ-unsaturated ketones broad scope. Particularly, chemoselective carbonylation diols further highlights practicability this protocol. The leverage as both coupling components activators for alcohol functionalization crucial method, thus no extraneous are required.

Transition metal-catalyzed enantioselective allylic transformations with electrophiles are widely recognized as a reliable method for synthesizing chiral small organic molecules, significantly impacting natural product synthesis and pharmaceutical development. In contrast to well-established linear-selective or branch-selective substitution through the judicious choice of transition metal catalyst, current addition carbonyls is primarily focused on γ-selective allylation. Achieving...

Enantioenriched unnatural amino acids represent a prevalent motif in organic chemistry, with profound applications biochemistry, medicinal and materials science. Herein, we report cobalt-catalyzed aza-Barbier reaction of dehydroglycines unactivated alkyl halides to afford α-amino esters high enantioselectivity. This catalytic reductive alkylative addition protocol circumvents the use moisture-, air-sensitive organometallic reagents, stoichiometric chiral auxiliaries, enabling conversion...

Abstract A palladium‐catalyzed domino spiro‐cyclization of carbamoyl chlorides with alkynes and benzynes, involving intramolecular C−H activation to afford valuable oxindole scaffolds bearing spiro quaternary stereocenters, has been developed. This one‐step synthesis spirooxindole is both step‐ atom‐economic, proceeding high regioselectivity in moderate excellent yields. magnified image

A direct transformation of aryl esters to secondary benzylic alcohols via tandem Ni-catalyzed cross-coupling reactions aromatic 2-pyridyl with alkyl zinc reagents and carbonyl group reduction by Ni–H species is achieved. Preliminary mechanistic studies reveal that the generated in situ β-hydride elimination Negishi reagents. The reaction catalyzed bench-stable nickel salts under mild conditions wide functional tolerance.

Comprehensive Summary Transition metal‐catalyzed carbometallation of unsaturated hydrocarbons constitutes one the most efficient synthetic methodologies for construction C—C bond. Recently, incorporation organometallic reagent with CO gas as a nucleophilic acyl synthon could enable acylmetallation reaction, which greatly increases horizon chemistry. Herein, we report nickel‐catalyzed regiodivergent acylzincation o ‐cyano cinnamate ester and styrene, in cyano moiety intramolecularly captures...

Abstract Chromium‐catalyzed enantioselective Nozaki–Hiyama–Kishi (NHK) reaction represents one of the most powerful approaches for formation chiral carbon‐heteroatom bond. However, construction sterically encumbered tetrasubstituted stereocenter through NHK still posts a significant challenge. Herein, we disclose cobalt‐catalyzed aza‐NHK ketimine with alkenyl halide to provide convenient synthetic approach manufacture enantioenriched α‐vinylic amino acid. This protocol exhibits excellent...