A nickel-catalyzed conjunctive cross-coupling between non-conjugated alkenes, aryl iodides, and alkylzinc reagents is reported. Excellent regiocontrol is achieved utilizing an 8-aminoquinoline directing group that can be readily cleaved to unmask net β,γ-dicarbofunctionalized carboxylic acid products. Under optimized conditions, both terminal and internal alkene substrates provided the corresponding alkyl/aryl difunctionalized products in moderate to excellent yields. The methodology developed herein represents the first three-component 1,2-dicarbofunctionalization of non-conjugated alkenes involving a C(sp)-C(sp) reductive elimination step.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jacs.7b06567 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
[Pd(NHC)(μ-Cl)Cl]: The Highly Reactive Air- and Moisture-Stable, Well-Defined Pd(II)-N-Heterocyclic Carbene (NHC) Complexes for Cross-Coupling Reactions.
Acc Chem Res
November 2024
Department of Chemistry, Rutgers University, 73 Warren Street, Newark, New Jersey 07102, United States.
Article Synopsis
- Palladium-catalyzed cross-coupling reactions are crucial in various fields like pharmaceuticals and materials science due to their ability to form C-C and C-X bonds selectively and efficiently.
- The development of new ligands and precatalysts, especially Pd(II)-N-heterocyclic carbene complexes, enhances reaction selectivity and reactivity while maintaining stability under mild conditions.
- The latest innovation includes the highly reactive chloro dimers of Pd(NHC) complexes, which can be easily synthesized in a one-pot process and are stable yet effective in catalyzing reactions.
Weak Base-Promoted Direct Cross-Coupling of Naphthalene-1,8-diaminato-substituted Arylboron Compounds.
JACS Au
October 2024
Graduate School of Advanced Science and Engineering, Hiroshima University, Higashi-Hiroshima 739-8526, Japan.
The indispensability of a base in Suzuki-Miyaura coupling (SMC) employing organoboronic acids/esters is well recognized, which occasionally induces competitive protodeborylation in organoboron reagents. This phenomenon is particularly pronounced in fluorine-substituted aryl and heteroaryl boron compounds. Here, we show that direct SMC of naphthalene-1,8-diaminato (dan)-substituted aryl boron compounds, Ar-B(dan), characterized by its remarkable stability toward protodeborylation due to their diminished boron-Lewis acidity, occurs utilizing a weak base in conjunction with a palladium/copper cooperative catalyst system.
View Article and Find Full Text PDFPerfect Partners: Biocatalytic Halogenation and Metal Catalysis for Protein Bioconjugation.
Chembiochem
December 2024
Organic and Bioorganic Chemistry, Department of Chemistry, Bielefeld University, Universitätsstraße 25, 33615, Bielefeld, Germany.
Flavin-dependent halogenases (FDHs) are the most extensively researched halogenases and show great potential for biotransformation applications. These enzymes use chloride, bromide, or iodide ions as halogen donors to catalyze the oxygen-dependent halogenation of electron-rich aryl moieties, requiring stochiometric amounts of FADH in the process. This makes FDH-catalyzed aryl halogenation a highly selective and environmentally friendly tool for the synthesis of aryl halides.
View Article and Find Full Text PDFCongested C(sp3)-rich architectures enabled by iron-catalysed conjunctive alkylation.
Nat Catal
March 2024
Department of Chemistry, National University of Singapore, 4 Science Drive 2, Republic of Singapore, 117544.
Catalytic cross-coupling by transition metals has revolutionized the formation of C-C bonds in organic synthesis. However, the challenge of forming multiple alkyl-alkyl bonds in crowded environments remains largely unresolved. Here, we report the regioselective functionalization of olefins with sp-hybridized organohalides and organozinc reagents using a simple (terpyridine)iron catalyst.
View Article and Find Full Text PDFEnantioselective Construction of Carbocyclic and Heterocyclic Tertiary Boronic Esters by Conjunctive Cross-Coupling Reaction.
J Am Chem Soc
August 2023
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, United States.
Synthesis of stereodefined carbocyclic and heterocyclic tertiary boronic esters is accomplished by performing a conjunctive cross-coupling reaction on preformed cyclic boron ate complexes. Boronates bearing spirocyclic and aryl bicyclic skeletons can be synthesized enantioselectively using a chiral PHOX-ligated Pd catalyst with achiral starting material, while substrates bearing continuous stereogenic centers can be generated diastereoselectively. A variety of aryl and alkenyl electrophiles are incorporated.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!