A detailed study of the Ni-catalyzed [4+3+2] cycloaddition reaction between ethyl cyclopropylideneacetate and dienynes has been conducted, resulting in the development of a new method for the synthesis of compounds containing nine-membered rings. We studied the reactivity of various dienynes, together with their substituent and conformational effects. The mechanism of the reaction was probed by examining the stoichiometric reactions of the Ni complexes and dienynes.
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http://dx.doi.org/10.1002/chem.201204087 | DOI Listing |
Nat Commun
January 2025
State Key Laboratory of Organometallic Chemistry, Shanghai of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, PR China.
Motivated by the inherent benefits of synergistically combining electrochemical methodologies with nickel catalysis, we present here a Ni-catalyzed enantioselective electroreductive cross-coupling of benzyl chlorides with aryl halides, yielding chiral 1,1-diaryl compounds with good to excellent enantioselectivity. This catalytic reaction can not only be applied to aryl chlorides/bromides, which are challenging to access by other means, but also to benzyl chlorides containing silicon groups. Additionally, the absence of a sacrificial anode lays a foundation for scalability.
View Article and Find Full Text PDFOrg Lett
January 2025
School of Pharmacy, Hangzhou Normal University, Hangzhou, Zhejiang 311121, P. R. China.
We demonstrate here an efficient and facile Ni-catalyzed electrochemical cross-electrophile thiolation approach for readily available alkyl alcohols with pyridyl thioesters. This C(sp)-S bond-forming modular strategy displays extensive substrate adaptability and good functional group tolerance, which allows the production of a range of alkyl sulfides with specific chemoselectivity. Furthermore, the potential applications of this methodology are illustrated by last-stage modification of bioactive molecules and sulfinylative cross-couplings.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Sichuan University, West China School of Pharmacy, Renmin Sout Road, 3rd Section, 17#, 610041, Chengdu, CHINA.
Bryostatins are a family of marine natural products that have garnered significant interests, as evidenced by over 40 clinical trials. However, their extremely low natural abundance has severely limited further research. Despite significant efforts, which have led to the total synthesis of seven bryostatin members by eight independent research groups, these complex molecules present persistent challenges for stereocontrolled, large-scale, and especially divergent synthesis.
View Article and Find Full Text PDFSci Adv
January 2025
State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China).
Singly occupied molecular orbital (SOMO) activation of in situ generated enamines has achieved great success in (asymmetric) α-functionalization of carbonyl compounds. However, examples on the use of this activation mode in the transformations of other functional groups are rare, and the combination of SOMO activation with transition metal catalysis is still less explored. In the area of deoxygenative functionalization of amides, intermediates such as iminium ions and enamines were often generated in situ to result in the formation of α-functionalized amines.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. China.
Quaternary carbon centers are widespread structural motifs, thus representing extensive interest in organic synthesis. We describe here an efficient nickel-catalyzed intermolecular, -selective arylation of minimally functionalized alkenes with stable organoborons, affording a broad range of cyclic or acyclic quaternary carbon centers under mild conditions. The utilization of the diimine ligand is critical for high reactivity and chemoselectivity.
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