Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

The debut of chiral cyclic (alkyl)(amino)carbenes (CAACs) in enantioselective catalysis.

ABSTRACT: The popularity of NHCs in transition metal catalysis has prompted the development of chiral versions as electron-rich neutral stereodirecting ancillary ligands for enantioselective transformations. Herein we demonstrate that cyclic (alkyl)(amino)carbene (CAAC) ligands can also engage in asymmetric transformations, thereby expanding the toolbox of available chiral carbenes.

SUBMITTER: Pichon D

PROVIDER: S-EPMC6761915 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

The debut of chiral cyclic (alkyl)(amino)carbenes (CAACs) in enantioselective catalysis.

Pichon Delphine D Soleilhavoup Michele M Morvan Jennifer J Junor Glen P GP Vives Thomas T Crévisy Christophe C Lavallo Vincent V Campagne Jean-Marc JM Mauduit Marc M Jazzar Rodolphe R Bertrand Guy G

Chemical science 20190706 33

The popularity of NHCs in transition metal catalysis has prompted the development of chiral versions as electron-rich neutral stereodirecting ancillary ligands for enantioselective transformations. Herein we demonstrate that cyclic (alkyl)(amino)carbene (CAAC) ligands can also engage in asymmetric transformations, thereby expanding the toolbox of available chiral carbenes. ...[more]

PMID: 31588330

Similar Datasets

CAAC-IPr*: easily accessible, highly sterically-hindered cyclic (alkyl)(amino)carbenes.

Project description:IPr* (IPr* = 1,3-bis(2,6-bis(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene) has emerged as a powerful highly hindered and sterically-flexible ligand platform for transition-metal catalysis. CAACs (CAAC = cyclic (al-kyl)(amino)carbenes) have gained major attention as strongly electron-rich carbon analogues of NHCs (NHC = N-heterocyclic carbene) with broad applications in both industry and academia. Herein, we report a merger of CAAC ligands with highly-hindered IPr*. The efficient synthesis, electronic characterization and application in model Cu-catalyzed hydroboration of alkynes is described. The ligands are strongly electron-rich, bulky and flexible around the N-Ar wingtip. The availability of various IPr* and CAAC templates offers a significant potential to expand the existing arsenal of NHC ligands to electron-rich bulky architectures with critical applications in metal stabilization and catalysis.

| S-EPMC9737351 | biostudies-literature

Gold(I) and Gold(III) Complexes of Cyclic (Alkyl)(amino)carbenes.

Project description:The chemistry of Au(I) complexes with two types of cyclic (alkyl)(amino)carbene (CAAC) ligands has been explored, using the sterically less demanding dimethyl derivative Me2CAAC and the 2-adamantyl ligand AdCAAC. The conversion of (AdCAAC)AuCl into (AdCAAC)AuOH by treatment with KOH is significantly accelerated by the addition of tBuOH. (AdCAAC)AuOH is a convenient starting material for the high-yield syntheses of (AdCAAC)AuX complexes by acid/base and C-H activation reactions (X = OAryl, CF3CO2, N(Tf)2, C2Ph, C6F5, C6HF4, C6H2F3, CH2C(O)C6H4OMe, CH(Ph)C(O)Ph, CH2SO2Ph), while the cationic complexes [(AdCAAC)AuL]+ (L = CO, CN t Bu) and (AdCAAC)AuCN were obtained by chloride substitution from (AdCAAC)AuCl. The reactivity toward variously substituted fluoroarenes suggests that (AdCAAC)AuOH is able to react with C-H bonds with pKa values lower than about 31.5. This, together with the spectroscopic data, confirm the somewhat stronger electron-donor properties of CAAC ligands in comparison to imidazolylidene-type N-heterocyclic carbenes (NHCs). In spite of this, the oxidation of Me2CAAC and AdCAAC gold compounds is much less facile. Oxidations proceed with C-Au cleavage by halogens unless light is strictly excluded. The oxidation of (AdCAAC)AuCl with PhICl2 in the dark gives near-quantitative yields of (AdCAAC)AuCl3, while [Au(Me2CAAC)2]Cl leads to trans-[AuCl2(Me2CAAC)2]Cl. In contrast to the chemistry of imidazolylidene-type gold NHC complexes, oxidation products containing Au-Br or Au-I bonds could not be obtained; whereas the reaction with CsBr3 cleaves the Au-C bond to give mixtures of [AdCAAC-Br]+[AuBr2]- and [(AdCAAC-Br)]+ [AuBr4]-, the oxidation of (AdCAAC)AuI with I2 leads to the adduct (AdCAAC)AuI·I2. Irrespective of the steric demands of the CAAC ligands, their gold complexes proved more resistant to oxidation and more prone to halogen cleavage of the Au-C bonds than gold(I) complexes of imidazole-based NHC ligands.

| S-EPMC4482412 | biostudies-literature

Metal-free dehydropolymerisation of phosphine-boranes using cyclic (alkyl)(amino)carbenes as hydrogen acceptors.

Project description:The divalent carbene carbon centre in cyclic (alkyl)(amino)carbenes (CAACs) is known to exhibit transition-metal-like insertion into E-H σ-bonds (E = H, N, Si, B, P, C, O) with formation of new, strong C-E and C-H bonds. Although subsequent transformations of the products represent an attractive strategy for metal-free synthesis, few examples have been reported. Herein we describe the dehydrogenation of phosphine-boranes, RR'PH·BH3, using a CAAC, which behaves as a stoichiometric hydrogen acceptor to release monomeric phosphinoboranes, [RR'PBH2], under mild conditions. The latter species are transient intermediates that either polymerise to the corresponding polyphosphinoboranes, [RR'PBH2]n (R = Ph; R' = H, Ph or Et), or are trapped in the form of CAAC-phosphinoborane adducts, CAAC·H2BPRR' (R = R' = tBu; R = R' = Mes). In contrast to previously established methods such as transition metal-catalysed dehydrocoupling, which only yield P-monosubstituted polymers, [RHPBH2]n, the CAAC-mediated route also provides access to P-disubstituted polymers, [RR'PBH2]n (R = Ph; R' = Ph or Et).

| S-EPMC6435733 | biostudies-literature

Aldiminium and 1,2,3-triazolium dithiocarboxylate zwitterions derived from cyclic (alkyl)(amino) and mesoionic carbenes

Project description: Not available

| S-EPMC10760461 | biostudies-literature

Realizing 1,1-Dehydration of Secondary Alcohols to Carbenes: Pyrrolidin-2-ols as a Source of Cyclic (Alkyl)(Amino)Carbenes.

Project description:Herein we report secondary pyrrolidin-2-ols as a source of cyclic (alkyl)(amino)carbenes (CAAC) for the synthesis of CAAC-CuI -complexes and cyclic thiones when reacted with CuI -salts and elemental sulfur, respectively, under reductive elimination of water from the carbon(IV)-center. This result demonstrates a convenient and facile access to CAAC-based CuI -salts, which are well known catalysts for different organic transformations. It further establishes secondary alcohols to be a viable source of carbenes-realizing after 185 years Dumas' dream who tried to prepare the parent carbene (CH2 ) by 1,1-dehydration of methanol. Addressed is also the reactivity of water towards CAACs, which proceeds through an oxidative addition of the O-H bond to the carbon(II)-center. This emphasizes the ability of carbon-compounds to mimic the reactivity of transition-metal complexes: reversible oxidative addition and reductive elimination of the O-H bond to/from the C(II)/C(IV)-centre.

| S-EPMC9400972 | biostudies-literature

Disclosing Cyclic(Alkyl)(Amino)Carbenes as One-Electron Reductants: Synthesis of Acyclic(Amino)(Aryl)Carbene-Based Kekule Diradicaloids.

Project description:Herein, we disclose cyclic(alkyl)(amino)carbenes (CAACs) to be one-electron reductants under the formation of a transient radical cation as indicated by EPR spectroscopy. The disclosed CAAC reducing reactivity was used to synthesize acyclic(amino)(aryl)carbene-based Thiele and Chichibabin hydrocarbons, a new class of Kekulé diradicaloids. The results demonstrate CAACs to be potent organic reductants. Notably, the acyclic(amino)(aryl)carbene-based Chichibabin's hydrocarbon shows an appreciable population of the triplet state at room temperature, as evidenced by both variable-temperature NMR and EPR spectroscopy.

| S-EPMC9321839 | biostudies-literature

Cr(i)Cl as well as Cr<sup>+</sup> are stabilised between two cyclic alkyl amino carbenes.

Project description:Cr(i)Cl is a very unstable species. The present work describes the stabilisation of Cr(i)Cl in the low coordinate environment of cyclic alkyl(amino) carbene ligands and its synthetic application to yield an unprecedented cationic complex with a two coordinate Cr(i). One electron reduction of (cAAC)2CrCl2 (1) with equivalent amount of KC8 results in the formation of (cAAC)2CrCl (2), with a distorted trigonal planar configuration at the metal centre. SQUID, EPR and theoretical studies reveal a Cr(i) centre with S = 5/2 spin ground state for 2. It represents the first example of a mononuclear Cr complex showing slow relaxation of magnetisation under an applied magnetic field. The chlorine atom in 2 is expected to be prone to further reactions with appropriate reagents. This qualifies 2 as a promising precursor for the preparation of various interesting complexes with Cr(i) in a low coordinate environment. The first example of this metathesis reaction is observed when 2 is treated with Na[B(C6H3(CF3)2)4] resulting in [(cAAC)2Cr]+[B(C6H3(CF3)2)4]-, a linear cationic complex with two coordinate Cr(i) and an S = 5/2 spin ground state.

| S-EPMC5490427 | biostudies-literature

Enantioselective conjugate silyl additions to cyclic and acyclic unsaturated carbonyls catalyzed by Cu complexes of chiral N-heterocyclic carbenes.

Project description:An efficient Cu-catalyzed protocol for enantioselective addition of a dimethylphenylsilanyl group to a wide range of cyclic and acyclic unsaturated ketones, esters, acrylonitriles, and alpha,beta,gamma,delta-dienones is disclosed. Reactions are performed in the presence of 1-2 mol % of commercially available and inexpensive CuCl, a readily accessible monodentate imidazolinium salt, and commercially available (dimethylphenylsilyl)pinacolatoboron. Cu-catalyzed enantioselective conjugate additions proceed to completion within only 2 h to afford the desired silanes in 87-97% yield and 90:10-99:1 enantiomeric ratio (er). Use of a proton source (e.g., MeOH) is not required; accordingly, synthetically versatile alpha-silyl boron enolates can be obtained. The special utility of the present protocol, in comparison with the related catalytic enantioselective aldol and boronate conjugate additions, is discussed and illustrated through various functionalizations of the enantiomerically enriched beta-silylcarbonyls.

| S-EPMC2836128 | biostudies-literature

Tackling N-Alkyl Imines with 3d Metal Catalysis: Highly Enantioselective Iron-Catalyzed Synthesis of α-Chiral Amines.

Project description:A readily activated iron alkyl precatalyst effectively catalyzes the highly enantioselective hydroboration of N-alkyl imines. Employing a chiral bis(oxazolinylmethylidene)isoindoline pincer ligand, the asymmetric reduction of various acyclic N-alkyl imines provided the corresponding α-chiral amines in excellent yields and with up to >99 % ee. The applicability of this base metal catalytic system was further demonstrated with the synthesis of the pharmaceuticals Fendiline and Tecalcet.

| S-EPMC7539954 | biostudies-literature

Activation of Ge-H and Sn-H Bonds with N-Heterocyclic Carbenes and a Cyclic (Alkyl)(amino)carbene.

Project description:A study of the reactivity of several N-heterocyclic carbenes (NHCs) and the cyclic (alkyl)(amino)carbene 1-(2,6-di-iso-propylphenyl)-3,3,5,5-tetramethyl-pyrrolidin-2-ylidene (cAACMe ) with the group 14 hydrides GeH2 Mes2 and SnH2 Me2 (Me=CH3 , Mes=1,3,5-(CH3 )3 C6 H2 ) is presented. The reaction of GeH2 Mes2 with cAACMe led to the insertion of cAACMe into one Ge-H bond to give cAACMe H-GeHMes2 (1). If 1,3,4,5-tetramethyl-imidazolin-2-ylidene (Me2 ImMe ) was used as the carbene, NHC-mediated dehydrogenative coupling occurred, which led to the NHC-stabilized germylene Me2 ImMe ⋅GeMes2 (2). The reaction of SnH2 Me2 with cAACMe also afforded the insertion product cAACMe H-SnHMe2 (3), and reaction of two equivalents Me2 ImMe with SnH2 Me2 gave the NHC-stabilized stannylene Me2 ImMe ⋅SnMe2 (4). If the sterically more demanding NHCs Me2 ImMe , 1,3-di-isopropyl-4,5-dimethyl-imidazolin-2-ylidene (iPr2 ImMe ) and 1,3-bis-(2,6-di-isopropylphenyl)-imidazolin-2-ylidene (Dipp2 Im) were employed, selective formation of cyclic oligomers (SnMe2 )n (5; n=5-8) in high yield was observed. These cyclic oligomers were also obtained from the controlled decomposition of cAACMe H-SnHMe2 (3).

| S-EPMC10100474 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data