A cobalt-catalyzed deuteration of amidoacrylates using deuterated methanol afforded α,β-dideuterio-α-amino esters in excellent enantiomeric ratios (mostly >95 : 5) and almost complete deuteration (99 %). The new protocol was used to prepare dideuterio-α-amino acid fragments in some drugs. Furthermore, the stereoselective deuteration was applied in a concise synthesis of dideuterio l-DOPA.
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http://dx.doi.org/10.1002/anie.202301091 | DOI Listing |
Angew Chem Int Ed Engl
November 2024
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore.
An operationally convenient cobalt-catalyzed one-pot one-step hydrosilylation/hydroboration reaction of arylidenecyclopropanes is developed to access racemic 1,4-borylsilylalkanes. In addition, the corresponding asymmetric reaction is developed with a chiral copper catalyst to prepare 1,4-borylsilylalkanes with high enantioselectivity by a one-pot two-step procedure. Mechanistic studies reveal that this difunctionalization process begins with metal-hydride-catalyzed ring-opening hydrosilylation of arylidenecyclopropanes to generate homoallylsilane intermediates, followed by regio- or enantioselective metal-hydride-catalyzed hydroboration of homoallylsilanes to produce skipped borylsilylalkanes.
View Article and Find Full Text PDFOrg Lett
October 2024
Jiangsu Key Laboratory of Neuropsychiatric Diseases and Department of Medicinal Chemistry, College of Pharmaceutical Sciences, Soochow University, 199 Ren-Ai Road, Suzhou, Jiangsu 215123, China.
Cobalt-catalyzed enantioconvergent cross-coupling of C(sp)-H bonds with -generated sulfenate anions is achieved to access chiral sulfoxides, which are found in the structures of many biologically active agents. The more challenging aliphatic C-H bonds as well as sterically hindered substrates containing tertiary C-H bonds could also be tolerated well. Mechanistic studies indicate that the transformation could undergo a CoS(O)R-mediated single-electron transfer with -fluorocarboxamides, followed by a 1,5-hydrogen atom transfer and then a pivotal organocobalt(IV)-controlled enantioselective cross-coupling process.
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science & Technology, 130 Meilong Road, Shanghai 200237, China.
Nat Commun
September 2024
State Key Laboratory of Chemo/Biosensing and Chemometrics, Advanced Catalytic Engineering Research Center of the Ministry of Education, College of Chemistry and Chemical Engineering, Hunan University, 410082, Changsha, Hunan, P. R. China.
J Am Chem Soc
September 2024
State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
Selective functionalization of ubiquitous C-H bonds based on 1,-metal migration provides an attractive and sustainable route to access complex molecules from readily available precursors. Herein, we report a Co-catalyzed asymmetric reductive migratory Nozaki-Hiyama-Kishi (NHK) coupling between two readily available electrophiles, aryl (pseudo)halides and aldehydes, via an unprecedented through-space aryl-to-alkenyl 1,4-cobalt/hydride shift. The judicious choice of ligands is crucial for selectivity, leading to either ipso- or migratory NHK products with exquisite control of regio-, /-, and enantioselectivity.
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