Photocatalyzed Annulation‐Biselenylation of Enynone with Diarylselenides toward Biselenium‐Substituted 1‐Indanones under Metal‐ and Photosensitizer‐Free Conditions

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 17, 2025

Comprehensive Summary A practical photocatalytic annulation‐biselenylation strategy has been developed for the efficient synthesis of biselenium‐substituted 1‐indanones (38 examples in total) with generally good yields (up to 95%) and excellent stereoselectivity (>19 : 1 Z / E ratio) by employing enynones diaryl selenides as starting materials under photosensitizer‐free conditions. The reaction mechanism involves a cascade process comprising homolytic cleavage, radical addition, 5‐ exo ‐ dig cyclization, capture, enabling sequential formation multiple bonds, such C(sp 3 )‐Se, )‐C(sp 2 ), )‐Se rapidly construct molecular complexity. Notably, this approach demonstrates wide substrate compatibility tolerability towards various functional groups. It is further characterized its remarkable efficiency creating chemical bonds achieving high atomic utilization 100%.

Language: Английский

Umpolung Reactivity of in Situ Derived Aryl Hydrazones: An Asymmetric Brønsted Acid Catalyzed Strategy to Access Fused Pyrazolidines

Organic Letters, Journal Year: 2024, Volume and Issue: 26(32), P. 6853 - 6858

Published: Aug. 1, 2024

Herein, we report an intriguing cascade strategy for synthesizing optically active fused pyrazolidines featuring three contiguous stereogenic centers. The formyl-tethered enones are templates the developed umpolung reactivity, showcasing diverse substrate adaptability with various arylhydrazines. chiral phosphoric acid catalyst offers stereochemical guidance, forming commendable to excellent stereoselectivities. Additionally, scalability, postsynthetic transformations, and instability of unacylated have been successfully demonstrated.

Language: Английский

Photoinduced Platinum-Catalyzed Reductive Allylation of α-Diketones with Allylic Carbonates

Organic Letters, Journal Year: 2024, Volume and Issue: 26(10), P. 2023 - 2028

Published: Feb. 29, 2024

A unique process for the photoinduced platinum-catalyzed reductive allylation of α-diketones with allylic carbonates has been developed. This reaction was found to proceed selectively at more electron-deficient carbonyl group diketone afford an α-keto homoallylic alcohol. Such products could be further derivatized by transformation remaining group. mechanistic investigation suggests that a ketyl radical generated in response photoirradiation reacts (π-allyl)platinum complex form C–C bond.

Language: Английский