Reductive Allylic Defluorinative Cross-Coupling Enabled by Ni/Ti Cooperative Catalysis.

Org Lett

Hefei National Laboratory for Physical Science at the Microscale, Department of Chemistry, Center for Excellence in Molecular Synthesis , University of Science and Technology of China, 96 Jinzhai Road , Hefei , Anhui 230026 , P. R. China.

Published: October 2019

Unactivated alkyl chlorides are abundant building blocks in organic synthesis, but they have been rarely engaged in cross-electrophile coupling. Herein, we report a Ni/Ti-cocatalyzed reductive allylic defluorinative cross-coupling between trifluoromethyl alkenes and unactivated alkyl chlorides and bromides, enabling the efficient preparation of diverse functional-group-rich -difluoroalkenes. Notably, synthesis of the -difluoroalkene analogues of azaperone, haloperidol, and benperidol was also accomplished using our method as a key step.

Download full-text PDF

Source
http://dx.doi.org/10.1021/acs.orglett.9b03102DOI Listing

Publication Analysis

Top Keywords

reductive allylic
8
allylic defluorinative
8
defluorinative cross-coupling
8
unactivated alkyl
8
alkyl chlorides
8
cross-coupling enabled
4
enabled ni/ti
4
ni/ti cooperative
4
cooperative catalysis
4
catalysis unactivated
4

Similar Publications

Chiral allylamines are important structural components in natural products, pharmaceuticals, and chiral catalysts. Herein, we report a cobalt-catalyzed enantioselective reductive coupling of imines with internal alkynes to synthesize chiral allylamines. The reaction is catalyzed by a cobalt complex derived from commercially available bisphosphine ligand utilizing zinc as the electron donor.

View Article and Find Full Text PDF

This study aimed to enhance the properties and compostability of active poly(lactic acid) (PLA) films by incorporating β-cyclodextrin (β-CD) inclusion complexes with allyl isothiocyanate (AITC). Films were prepared using melt extrusion and characterized based on their structural, chemical, morphological, thermal, and barrier properties. These inclusion complexes improved the thermal stability and moisture absorption of films, enhancing disintegration under composting conditions.

View Article and Find Full Text PDF

Chemodivergent, enantio- and regioselective couplings of alkynes, aldehydes and silanes enabled by nickel/N-heterocyclic carbene catalysis.

Sci Bull (Beijing)

December 2024

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China. Electronic address:

Divergent synthesis of valuable molecules through common starting materials and metal catalysis represents a longstanding challenge and a significant research goal. We here describe chemodivergent, highly enantio- and regioselective nickel-catalyzed reductive and dehydrogenative coupling reactions of alkynes, aldehydes, and silanes. A single chiral Ni-based catalyst is leveraged to directly prepare three distinct enantioenriched products (silyl-protected trisubstituted chiral allylic alcohols, oxasilacyclopentenes, and silicon-stereogenic oxasilacyclopentenes) in a single chemical operation.

View Article and Find Full Text PDF

Cobalt-catalyzed reduction of esters to alkanes.

Chem Commun (Camb)

January 2025

School of Chemical Sciences, National Institute of Science Education and Research (NISER), An OCC of Homi Bhabha National Institute, Bhubaneswar-752050, India.

The reduction of aryl carboxylates to methyl and allyl arene was attained using a well-defined cobalt catalyst. This catalytic transformation employs only a sub-stoichiometric amount of base, and diethylsilane as a reductant. Catalytic activation of the Si-H bond of the silanes, C-O bond of the ester, and silyl ether intermediates by cobalt is crucial to achieving exhaustive reduction.

View Article and Find Full Text PDF

Using amines in catalytic transfer hydrogenation (TH) is challenging, despite their potential availability as a hydrogen source. Here, we describe a photoredox/nickel-catalyzed TH of alkyne through an intermediary aminoalkyl Ni species. This reaction successfully provided functionalized ()-alkenes, such as (homo)allyl ethers, alcohols, and amides (/ = up to >99:1), and the reaction thus bypasses a limitation of substrate scope in TH using amine and a Lindlar catalyst.

View Article and Find Full Text PDF

Want 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!