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.
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http://dx.doi.org/10.1021/acs.orglett.9b03102 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur, 741246, West Bengal, India.
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 PDFMolecules
December 2024
Department of Analytical Chemistry, Nutrition & Food Sciences, University of Alicante, 03690 Alicante, Spain.
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 PDFSci 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 PDFChem 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 PDFJ Org Chem
January 2025
Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan.
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.
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