A redox-neutral mild methodology for the allylic C-H alkylation of unactivated alkenes with diazo compounds is demonstrated. The developed protocol is able to bypass the possibility of the cyclopropanation of an alkene upon its reaction with the acceptor-acceptor diazo compounds. The protocol is highly accomplished due to its compatibility with various unactivated alkenes functionalized with different sensitive functional groups. A rhodacycle π-allyl intermediate has been synthesized and proved to be the active intermediate. Additional mechanistic investigations aided the elucidation of the plausible reaction mechanism.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/acs.orglett.2c04356 | DOI Listing |
J Org Chem
January 2025
School of Pharmacy, Hangzhou Medical College, 8 Yikang Road, Hangzhou 311300, PR China.
A Fe-catalyzed hydrocyclization reaction of unactivated alkenes was developed, utilizing PhSiH as the hydrogen source, yielding 2,3-dihydroquinazolinone (DHQZ) derivatives in moderate to good yields. Notably, when the substrate was switched to -cyano--(2-(prop-1-en-2-yl)phenyl)benzamides, the reaction yielded only the unreduced products. Mechanistic studies revealed that the intramolecular addition of the in situ formed radical to the unactivated alkene results in the formation of the fused ring.
View Article and Find Full Text PDFNat Commun
January 2025
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, PR China.
Allylic ethers and alcohols are essential structural motifs commonly present in natural products and pharmaceuticals. Direct allylic C-H oxygenation of internal alkenes is one of the most direct methods, bypassing the necessity for an allylic leaving group that is needed in the traditional Tsuji-Trost reaction. Herein, we develop an efficient and practical method for synthesizing (E)-allyl ethers from readily available internal alkenes and alcohols or phenols via selective allylic C-H oxidation.
View Article and Find Full Text PDFEnviron Technol
January 2025
State Key Laboratory of Heavy Oil Processing, Beijing Key Lab of Oil & Gas Pollution Control, China University of Petroleum-Beijing, Beijing, People's Republic of China.
Oxidants used in the ISCO technology usually require activation by activators to degrade contaminants. However, this study investigated degradation of 15 typical halogenated hydrocarbons by five common ISCO oxidants (PS, PMS, HO, KMnO, SPC) without activation in both pure water and real groundwater. Unactivated PS could degrade 14 halogenated hydrocarbons, excluding tetrachloromethane.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Department of Chemistry, Zhejiang University, Hangzhou, 310058, China.
Heck silylation of unactivated alkenes is an efficient strategy for the synthesis of useful organosilicon compounds. However, extensive efforts have been dedicated to only achieving achiral molecules. Herein, a highly regio- and enantioselective cobalt-catalyzed Heck silylation of unactivated alkenes with hydrosilanes is reported for the first time, providing access to axially chiral alkenes in good to excellent yields with 87-98 % ee.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Advanced Catalysis and Green Manufacturing Collaborative Innovation Center, School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China.
A visible-light-promoted azidation/arylation of unactivated alkenes with Togni-N has been achieved, leading to a series of azidated pyrrolo[1,2-]indoles under photocatalyst-free conditions. Notably, an EDA complex derived from the electron-rich indole derivatives and Togni-N served as the key intermediate in this reaction.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!