Herein, a facile method is developed for the synthesis of vicinal bisphosphine derivatives based on a cascade of hydrophosphinylation, elimination, and hydrophosphinylation of secondary phosphine oxides with nitroalkenes. This cascade reaction provides step-economy access to a series of vicinal bisphosphine derivatives with high to excellent yields (up to 99%). This method was further extended to prepare, in one-pot, regioselective vicinal bisphosphine derivatives that incorporated two different phosphorus functional groups.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.orglett.3c04297 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Regioselective One-Pot Synthesis of Vicinal Bisphosphine Derivatives from Nitroalkenes by Hydrophosphinylation/Elimination/Hydrophosphinylation.
Org Lett
March 2024
Tokyo University of Pharmacy and Life Sciences, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan.
Herein, a facile method is developed for the synthesis of vicinal bisphosphine derivatives based on a cascade of hydrophosphinylation, elimination, and hydrophosphinylation of secondary phosphine oxides with nitroalkenes. This cascade reaction provides step-economy access to a series of vicinal bisphosphine derivatives with high to excellent yields (up to 99%). This method was further extended to prepare, in one-pot, regioselective vicinal bisphosphine derivatives that incorporated two different phosphorus functional groups.
View Article and Find Full Text PDFLigand-Dictated Regiodivergent Allylic Functionalizations via Palladium-Catalyzed Remote Substitution.
Angew Chem Int Ed Engl
July 2023
CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032, China.
Different from classical allylic substitutions that require a vicinal leaving group, an olefin bearing a remote leaving group is scarcely viewed as a potential allylation substrate. Herein, we describe feasible protocols to achieve regiodivergent allylic C-H functionalizations via palladium-catalyzed remote substitution, which provides a novel strategy for the seldomly studied migratory Tsuji-Trost reaction. Dictated by a suitable ligand, a process that involved 4,3-hydrofunctionalization of the generated conjugated diene intermediate via metal walking is observed in generally >20 : 1 regioselectivity.
View Article and Find Full Text PDFCatalytic Asymmetric Mannich Reaction of α-Fluoronitriles with Ketimines: Enantioselective and Diastereodivergent Construction of Vicinal Tetrasubstituted Stereocenters.
ACS Catal
March 2019
Department of Chemistry, Georgetown University, 37th and O Streets, Washington, DC 20057, USA.
Diastereodivergent and enantioselective conversion of isatin ketimines to α-fluoro-β-aminonitriles with vicinal tetrasubstituted stereocenters is achieved by a chiral copper complex/guanidine base catalyzed Mannich reaction with proper choice of the bisphosphine ligand. The reaction is broad in scope, scalable, and provides efficient access to a series of 3-aminoindolinones exhibiting a quaternary carbon-fluorine stereocenter with high yields and stereoselectivities. Selective transformations of the Mannich reaction products into multifunctional 3-aminooxindoles without erosion of enantiomeric and diastereomeric purity highlight the synthetic utility.
View Article and Find Full Text PDFPractical, efficient, and broadly applicable synthesis of readily differentiable vicinal diboronate compounds by catalytic three-component reactions.
Tetrahedron
August 2017
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
A practical, efficient and broadly applicable catalytic method for synthesis of easily differentiable vicinal diboronate compounds is presented. Reactions are promoted by a combination of PCy or PPh, CuCl and LiO-Bu and may be performed with readily accessible alkenyl boronate substrates. Through the use of an alkenyl-B(pin) (pin = pinacolato) or alkenyl- B(dan) (dan = naphthalene-1,8-diaminato) starting material and commercially available (pin)B- B(dan) or B(pin) as the reagent, a range of vicinal diboronates, including those that contain a B-substituted quaternary carbon center, may be prepared in up to 91% yield and with >98% site selectivity.
View Article and Find Full Text PDFThe Viability of C5-Protonated- and C4,C5-Ditopic Carbanionic Abnormal NHCs: A New Dimension in NHC Chemistry.
Chemistry
March 2018
Anorganische Molekülchemie und Katalyse, Lehrstuhl für, Anorganische Chemie und Strukturchemie, Centrum für, Molekulare Materialien, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25, 33615, Bielefeld, Germany.
The first C5-protonated abnormal N-heterocyclic carbene (aNHC), PhC{N(2,6-iPr C H )} CHC: (4) is readily accessible by C4-deprotonation of [ArC{N(2,6-iPr C H )} CHCH]X (3 a-X) (Ar=Ph, X=Br or I) with a base. The aNHC 4 is stable at 298 K in [D ]THF solution and has been spectroscopically characterized. The facile availability of 4 enables the synthesis of a series of main-group compounds as well as transition-metal complexes featuring a new phosphorus-aNHC hybrid ligand.
View Article and Find Full Text PDFWant 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!