An efficient phosphaannulation by Pd-catalyzed carbonylation of C-H bonds of phosphonic and phosphinic acids for the synthesis of oxaphosphorinanone oxides is reported. These compounds are novel phosphorus heterocyclic scaffolds, thus opening a new avenue to sequential C-C/C-O bond formation in one pot.
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http://dx.doi.org/10.1021/ol501066k | DOI Listing |
Org Biomol Chem
January 2025
College of Chemistry and Pharmaceutical Engineering, Nanyang Normal University, Nanyang, 473061, P. R. China.
A highly practical and efficient Cp*Co(III)-catalyzed C-H alkylation/alkenylation reaction of anilides with maleimides and acrylates was developed, during which a weakly coordinating amide carbonyl group functioned as the directing group. This approach features high efficiency, good functional group tolerance, and broad substrate scope, and a variety of 3-substituted succinimides and -alkenylated anilides were synthesized in moderate to excellent yields. Furthermore, the reaction is highly selective, affording mono--alkylated/alkenylated products only.
View Article and Find Full Text PDFAcc Chem Res
January 2025
Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, China.
ConspectusThe Mannich reaction, involving the nucleophilic addition of an enol(ate) intermediate to an imine or iminium ion, is one of the most widely used synthetic methods for the synthesis of β-amino carbonyl compounds. Nevertheless, the homo-Mannich reaction, which utilizes a homoenolate intermediate as the nucleophilic partner and provides straightforward access to the valuable γ-amino carbonyl compounds, remains underexplored. This can be largely attributed to the difficulties in generation and manipulation of the homoenolate species, despite various homoenolate equivalents that have been developed.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, University of Houston, Houston, Texas 77204-5003, United States.
Monoanionic, bidentate-auxiliary-directed, cobalt-catalyzed C-H bond functionalization has become a very useful tool in organic synthesis. A comprehensive investigation into isolated organometallic intermediates and their reactivity within the catalytic cycle is lacking. We report here mechanistic studies of cobalt-catalyzed, aminoquinoline-directed C(sp)-H bond functionalization.
View Article and Find Full Text PDFChem Sci
December 2024
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford South Parks Road Oxford OX1 3QR UK
The reaction chemistry of an unprecedented 'inorganic cumulene' - featuring a five-atom BNBNB chain - towards C[double bond, length as m-dash]O (and related) multiple bonds is disclosed. In marked contrast to related all-carbon systems, the intrinsic polarity of the BNBNB chain (featuring electron-rich nitrogen and electron-deficient boron centres) enables metathesis chemistry with electrophilic heteroallenes such as CO and with organic carbonyl compounds. Transfer of the borylimide unit to [CO], [CS], [PP{(NDippCH)}] and [C(H)Ph] moieties generates (boryl)N[double bond, length as m-dash]C[double bond, length as m-dash]X systems (X = O, S, PP{(NDippCH)}, C(H)Ph), driven thermodynamically by B-O bond formation.
View Article and Find Full Text PDFJ Org Chem
January 2025
Institute of Chemistry, Technical University of Berlin, Straße des 17. Juni 115, 10623 Berlin, Germany.
Chiral heterocyclic alcohols and amines are frequently used building blocks in the synthesis of fine chemicals and pharmaceuticals. Herein, we report a one-pot photoenzymatic synthesis route for -Boc-3-amino/hydroxy-pyrrolidine and -Boc-4-amino/hydroxy-azepane with up to 90% conversions and >99% enantiomeric excess. The transformation combines a photochemical oxyfunctionalization favored for distal C-H positions with a stereoselective enzymatic transamination or carbonyl reduction step.
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