The first deoxygenative Heck reactions are described, as illustrated by formate-mediated -substitutions of vinyl triflates with aryl iodides. The collective data corroborate a mechanism in which Pd(OAc) and BuNI form the dianionic iodide-bridged dimer [PdI][NBu], which, under reducing conditions, serves as a precursor to the palladium(I) complex [PdI][NBu]. Dinculear oxidative addition of aryl iodide forms [PdI(Ar)][NBu], which dissociates to the monometallic complex [PdI(Ar)][NBu]. Vinyl triflate migratory insertion-sulfonate elimination delivers a palladium(IV) carbene, which upon β-hydride elimination/C-H reductive elimination gives the product of -substitution. These processes are the first efficient formate-mediated cross-electrophile reductive couplings beyond carbonyl addition.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC10615887 | PMC |
| http://dx.doi.org/10.1021/jacs.3c09876 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Alcohols as Alkyl Electrophiles for Deoxygenative Heck Reaction Enabled by Excited State Pd Catalysis.
Org Lett
October 2024
School of Chemistry and Chemical Engineering, Anhui Province Key Laboratory of Advanced Catalytic Materials and Reaction Engineering, Department Flexible Composite Materials Key Technology Center, Hefei University of Technology, Hefei 230009, China.
Here, we present a general method for the photoinduced Pd-catalyzed deoxygenative Heck reaction of vinyl arenes with -iodophenyl-thionocarbonate derived from alcohols. Mechanistic studies reveal that the deoxygenation involves a 5--trig cyclization and fragmentation process, with radical addition identified as the rate-determining step in this transformation. This one-pot procedure demonstrates excellent selectivity for less hindered hydroxyl groups in diols, facilitating late-stage functionalization of complex molecules and scalability to gram-scale synthesis.
View Article and Find Full Text PDFDivergent Transformations of Aromatic Esters: Decarbonylative Coupling, Ester Dance, Aryl Exchange, and Deoxygenative Coupling.
Acc Chem Res
June 2024
Department of Applied Chemistry, Waseda University, 513 Wasedatsurumakicho, Shinjuku, Tokyo 162-0041, Japan.
ConspectusAromatic esters are cost-effective, versatile, and commonly used scaffolds that are readily synthesized or encountered as synthetic intermediates. While most conventional reactions involving these esters are nucleophilic acyl substitutions or 1,2-nucleophilic additions─where a nucleophile attacks the carbonyl group, decarbonylative transformations offer an alternative pathway by using the carbonyl group as a leaving group. This transition-metal-catalyzed process typically begins with oxidative addition of the C(acyl)-O bond to the metal.
View Article and Find Full Text PDFPalladium(I)-Iodide-Catalyzed Deoxygenative Heck Reaction of Vinyl Triflates: A Formate-Mediated Cross-Electrophile Reductive Coupling with -Substitution.
J Am Chem Soc
October 2023
Department of Chemistry, University of Texas at Austin, Austin, Texas 78712, United States.
The first deoxygenative Heck reactions are described, as illustrated by formate-mediated -substitutions of vinyl triflates with aryl iodides. The collective data corroborate a mechanism in which Pd(OAc) and BuNI form the dianionic iodide-bridged dimer [PdI][NBu], which, under reducing conditions, serves as a precursor to the palladium(I) complex [PdI][NBu]. Dinculear oxidative addition of aryl iodide forms [PdI(Ar)][NBu], which dissociates to the monometallic complex [PdI(Ar)][NBu].
View Article and Find Full Text PDFThe six-membered heterocycles containing oxygen and nitrogen (tetrahydropyrans, pyrans, piperidines) are among the most common heterocyclic structures ubiquitously present in bioactive molecules such as carbohydrates, small-molecule drugs, and natural products. Chemical synthesis of fully functionalized pyrans and piperidines is a research theme of practical importance and scientific significance and, thus, has attracted continuous interest from synthetic chemists. Among the numerous synthetic approaches, Achmatowicz rearrangement (AchR) represents a general and unique strategy that uses biomass-derived furfuryl alcohols as the renewable starting material to obtain fully functionalized six-membered oxygen/nitrogen heterocycles, which provides golden opportunities for organic chemists to address various synthetic challenges.
View Article and Find Full Text PDFAsymmetric Total Syntheses of (-)-Hedycoropyrans A and B.
J Org Chem
January 2017
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China.
The first and asymmetric total synthesis of (-)-hedycoropyrans A (1) was accomplished in 18 steps with 5.4% overall yield. The key features of our strategy include (1) construction of the unusual trans-2-aryl-6-alkyl tetrahydropyran core via Achmatowicz rearrangement, Zn-mediated reductive deoxygenation, and Heck-Matsuda coupling reaction, and (2) installation of 3,4-anti-dihydroxy from the corresponding 3,4-syn-dihydroxy THP through chemo- and regioselective IBX oxidation and Evans-Saksena reduction.
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!