Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Rhodium-catalyzed C-H functionalization-based approach to eight-membered lactams.

ABSTRACT: A Rh(iii) catalyzed formal [4 + 2 + 2] cyclization of N-pivaloyloxybenzamides 1 with 1,6-allene-enes 2 by C-H functionalization is reported. The reactions occur at room temperature and are compatible with air and moisture with a tolerance of many synthetically useful functional groups. The follow-up modifications of the products have been demonstrated. After careful mechanistic studies and DFT calculation, a reaction mechanism was proposed.

SUBMITTER: Wu S

PROVIDER: S-EPMC5645731 | biostudies-literature | 2015 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Rhodium-catalyzed C-H functionalization-based approach to eight-membered lactams.

Wu Shangze S Zeng Rong R Fu Chunling C Yu Yihua Y Zhang Xue X Ma Shengming S

Chemical science 20150205 4

A Rh(iii) catalyzed formal [4 + 2 + 2] cyclization of N-pivaloyloxybenzamides 1 with 1,6-allene-enes 2 by C-H functionalization is reported. The reactions occur at room temperature and are compatible with air and moisture with a tolerance of many synthetically useful functional groups. The follow-up modifications of the products have been demonstrated. After careful mechanistic studies and DFT calculation, a reaction mechanism was proposed. ...[more]

PMID: 29308141

Similar Datasets

Rhodium(I)-catalyzed allenic carbocyclization reaction affording delta- and epsilon-lactams.

Project description:This letter extends the scope of the rhodium(I)-catalyzed allenic Alder-ene carbocyclization reaction to the preparation of delta- and epsilon-lactams from amides. A variety of allenic propiolamides were cycloisomerized to give a number of unsaturated delta-lactams. In addition, allenic propargylamides give good yields of the corresponding epsilon-lactams. Formation of lactams possessing these ring sizes has rarely been accomplished via transition-metal-catalyzed carbon-carbon bond forming strategies. Thus, this approach provides an alternative strategy for synthesizing these substructures. [reaction: see text].

| S-EPMC3266663 | biostudies-literature

Rhodium(II)-catalyzed enantioselective C-H functionalization of indoles.

Project description:A catalytic, enantioselective method for the C-H functionalization of indoles by diazo compounds has been achieved. With catalytic amounts of Rh(2)(S-NTTL)(4), the putative Rh-carbene intermediates from α-alkyl-α-diazoesters react with indoles at C(3) to provide α-alkyl-α-indolylacetates in high yield and enantioselectivity. From DFT calculations, a mechanism is proposed that involves a Rh-ylide intermediate with oxocarbenium character.

| S-EPMC3144986 | biostudies-literature

Geminal group-directed olefinic C-H functionalization via four- to eight-membered exo-metallocycles.

Project description:Great efforts have been made in the activation of a C(alkenyl)-H bond vicinal to the directing group to proceed via five- or six-membered endo-metallocycles. In stark contrast, functionalization of a C(alkenyl)-H bond geminal to the directing group via exo-metallocycle pathway continued to be elusive. Here we report the selective transformation of an olefinic C-H bond that is geminal to the directing group bearing valuable hydroxyl, carbamate or amide into a C-C bond, which proceeds through four- to eight-membered exo-palladacycles. Compared to the reported mechanisms proceeding only through six-membered exo-palladacycles via N,N-bidentate chelation, our weak and O-monodentate chelation-assisted C(alkenyl)-H activations tolerate longer or shorter distances between the olefinic C-H bonds and the coordinating groups, allowing for the functionalizations of many olefinic C-H bonds in alkenyl alcohols, carbamates and amides. The synthetic applicability has been demonstrated by the preparative scale and late-stage C-H functionalization of steroid and ricinoleate derivatives.

| S-EPMC6841671 | biostudies-literature

Regio- and Stereoselective Rhodium(II)-Catalyzed C-H Functionalization of Cyclobutanes.

Project description:Recent developments in controlled C-H functionalization transformations continue to inspire new retrosynthetic disconnections. One tactic in C-H functionalization is the intermolecular C-H insertion reaction of rhodium bound carbenes. These intermediates can undergo highly selective transformations through the modulation of the ligand framework of the rhodium catalyst. This work describes our continued efforts towards differentiating C-H bonds in the same molecule by judicious catalyst choice. Substituted cyclobutanes which exist as a mixture of interconverting conformers and possess neighboring C-H bonds within a highly strained framework are the targets herein for challenging the current suite of catalysts. While most C-H functionalization tactics focus on generating 1,2-disubstituted cyclobutanes via substrate-controlled directing group methods, the regiodivergent methods in this paper provide access to chiral 1,1-disubstituted and cis-1,3-disubstituted cyclobutanes simply by changing the catalyst identity, thus permitting entry to novel chemical space.

| S-EPMC7233328 | biostudies-literature

Rhodium(III)-catalyzed arylation of Boc-imines via C-H bond functionalization.

Project description:The first rhodium-catalyzed arylation of imines proceeding via C-H bond functionalization is reported. Use of a non-coordinating halide abstractor is important to obtain reactivity. Aryl-branched N-Boc-amines are formed, and a wide range of functionality is compatible with the reaction.

| S-EPMC3045530 | biostudies-literature

Rhodium-catalyzed C-H functionalization of heteroarenes using indoleBX hypervalent iodine reagents.

Project description:The C-H indolation of heteroarenes was realized using the benziodoxolone hypervalent iodine reagents indoleBXs. Functionalization of the C-H bond in bipyridinones and quinoline N-oxides catalyzed by a rhodium complex allowed to incorporate indole rings into aza-heteroaromatic compounds. These new transformations displayed complete regioselectivity for the C-6 position of bipyridinones and the C-8 position of quinoline N-oxides and tolerated a broad range of functionalities, such as halogens, ethers, or trifluoromethyl groups.

| S-EPMC6009173 | biostudies-literature

Rhodium(III)-catalyzed indazole synthesis by C-H bond functionalization and cyclative capture.

Project description:An efficient, one-step, and highly functional group-compatible synthesis of substituted N-aryl-2H-indazoles is reported via the rhodium(III)-catalyzed C-H bond addition of azobenzenes to aldehydes. The regioselective coupling of unsymmetrical azobenzenes was further demonstrated and led to the development of a new removable aryl group that allows for the preparation of indazoles without N-substitution. The 2-aryl-2H-indazole products also represent a new class of readily prepared fluorophores for which initial spectroscopic characterization has been performed.

| S-EPMC3656829 | biostudies-literature

Rhodium-catalyzed ring expansion of cyclopropanes to seven-membered rings by 1,5 C-C bond migration.

Project description: Not available

| S-EPMC3329940 | biostudies-literature

Rhodium(III)-catalyzed alkenyl C-H bond functionalization: convergent synthesis of furans and pyrroles.

Project description:Ring in the new: a new annulation for the efficient synthesis of substituted furans and pyrroles is reported. The Rh(III) -catalyzed reaction of O-methyl α,β-unsaturated oximes with aldehydes and N-tosyl imines affords secondary alcohol and amine intermediates, respectively. Cyclization and aromatization occurs under the reaction conditions to provide access to biologically relevant furans and pyrroles in good yields. Cp*=C(5)Me(5), DCE=1,2-dichloroethane, THF=tetrahydrofuran.

| S-EPMC3770945 | biostudies-literature

Enantioselective Synthesis of Spiroindenes by Enol-Directed Rhodium(III)-Catalyzed C-H Functionalization and Spiroannulation.

Project description:Chiral cyclopentadienyl rhodium complexes promote highly enantioselective enol-directed C(sp(2))-H functionalization and oxidative annulation with alkynes to give spiroindenes containing all-carbon quaternary stereocenters. High selectivity between two possible directing groups, as well as control of the direction of rotation in the isomerization of an O-bound rhodium enolate into the C-bound isomer, appear to be critical for high enantiomeric excesses.

| S-EPMC4648053 | 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