A mild and metal-free regiodivergent addition of carbon nucleophiles to α,β-unsaturated electrophiles was developed. Total 1,2-regioselectivity was observed in the addition of nitrobenzyl chloride derivative to α,β-unsaturated aldehydes in the presence of TDAE. Moreover, the reaction between -nitrobenzyl chloride and α,β-unsaturated iminium salts led to the formation of the 1,4-adduct with total regioselectivity.
Download full-text PDF |
Source |
---|---|
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6152382 | PMC |
http://dx.doi.org/10.3390/molecules22071178 | DOI Listing |
Chemistry
December 2024
Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Translational Research Hub, Maindy Road, Cathays, Cardiff, Cymru/Wales, CF24 4HQ, UK.
Precise control of selective alkene functionalization is a continuing challenge in the chemical community. In this study, we develop a substitution-controlled regiodivergent thioetherification of di- or trisubstituted alkenes using 10 mol % tris(pentafluorophenyl)borane [B(CF)] as a catalyst and N-thiosuccinimide as a sulfenylating reagent. This metal-free borane catalyzed C-S bond forming method is utilized for a Csp-H sulfenylation reaction to synthesize an array of diphenylvinylsulfide derivatives with good to excellent yields (25 examples, up to 91 % yield).
View Article and Find Full Text PDFJ Org Chem
September 2024
Urumqi Key Laboratory of Green Catalysis and Synthesis Technology, Key Laboratory of Oil and Gas Fine Chemicals, Ministry of Education & Xinjiang Uygur Autonomous Region, State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources, College of Chemistry, Xinjiang University, Urumqi 830017, PR China.
A metal-free, light-induced regiodivergent functionalization of α,β-unsaturated amides with aryltriazenes under ambient conditions was developed. The visible light and B(CF) cocatalyzed radical cascade arylation/cyclization of -alkyl--arylmethacrylamides can obtain functionalized 3,3-disubstituted oxindoles with the assistance of photocatalyst eosin Y-Na. In the absence of any catalyst, with purple light irradiation and electron-donor-acceptor (EDA) complex initiation, the radical cascade arylation/hydroxylation of -arylmethacrylamides affords α-hydroxylamides.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
April 2024
Laboratoire d'Innovation Moléculaire et Applications (UMR CNRS 7042), Université de Strasbourg/Université de Haute Alsace, ECPM 25 rue Becquerel, 67087, Strasbourg, France.
Regiodivergent reactions are a fascinating tool to rapidly access molecular diversity while using identical coupling partners. We have developed a new approach for regiodivergent synthesis using the dual character of hypervalent bromines. In addition to the recently reported reactivity of hypervalent bromines as aryne precursors, the first transition metal-catalyzed reaction is reported.
View Article and Find Full Text PDFNew J Chem
September 2023
Department of Chemistry and Physics, Florida Gulf Coast University, Fort Myers, Florida, 33965, USA.
Sulfones are fascinating and highly used functional groups, but current syntheses still have limitations. Here, a regiodivergent transition metal-free approach towards sulfones [()-allylic sulfones and α-sulfonyl-methyl styrenes] is reported. The method employs commercially available olefins, bases, additives, solvents, and sodium sulfinates (RSONa) and produces adducts in good yields.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
February 2024
School of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
An arylation protocol for pyridines is described, via the ring-opened Zincke intermediate. Treatment of pyridines with triflic anhydride and a secondary amine produces an azahexatriene species, which undergoes regioselective Pd-catalyzed arylation at the putative C4 position. Recyclization then provides the pyridine products.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!