Phosphine‐Catalyzed Divergent γ,γ‐ and ε,γ‐Umpolung Domino Additions of Bisoxindoles with Allenoates: Construction of Vicinal All‐Carbon Quaternary Stereocenters and Formal Total Synthesis of Dimeric Cyclotryptamine Alkaloids

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

Published: Jan. 25, 2025

Comprehensive Summary Vicinal all‐carbon quaternary stereocenters are widely present in natural products and bioactive molecules. However, the construction of such motif one step from readily available starting materials remains a significant challenge. Herein, we report phosphine‐catalyzed divergent γ,γ‐ ε,γ‐umpolung domino addition bisoxindoles with allenoates. This method serves as practical tool for concise synthesis series bisoxindole derivatives bearing sterically hindered vicinal under mild reaction conditions. The applicability this novel was demonstrated gram‐scale three known advanced intermediates total syntheses calycanthine, chimonanthine folicanthine.

Language: Английский

---

Recent advances in three-component radical acylative difunctionalization of unsaturated carbon–carbon bonds

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(18), P. 4488 - 4515

Published: Jan. 1, 2023

This review highlights the recent advances in radical acylated difunctionalization of unsaturated carbon–carbon bonds and focuses on mechanistic insights these transformations.

Language: Английский

---

Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(17), P. 10192 - 10280

Published: Aug. 8, 2024

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated

Language: Английский

---

Regioselective Hydro(deutero)silylation of 1,3-Enynes Enabled by Photoredox/Nickel Dual Catalysis

Organic Letters, Journal Year: 2024, Volume and Issue: 26(2), P. 536 - 541

Published: Jan. 5, 2024

In the presence of visible light irradiation, organophoto/nickel dual catalysts, and mild base K2HPO4, 1,3-enynes react with silanecarboxylic acids to give corresponding α-silylallenes high selectivity. this uniquely decarboxylative hydrosilylation 1,3-enynes, a silyl radical process is involved diverse electron-rich -poor substrates proceed smoothly in moderate excellent yields. This transformation particularly synthetically worthwhile when using MeOD as solvent, which furnishes new access α-silyldeuteroallenes.

Language: Английский

---

Challenging Task of Ni-Catalyzed Highly Regio-/Enantioselective Semihydrogenation of Racemic Tetrasubstituted Allenes via a Kinetic Resolution Process

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7419 - 7430

Published: March 6, 2024

The first earth-abundant transition metal Ni-catalyzed highly regio- and enantioselective semihydrogenation of racemic tetrasubstituted allenes via a kinetic resolution process as challenging task was well established. This protocol furnishes expedient access to diversity structurally important enantioenriched chiral allylic molecules with high regio-, enantio-, Z/E-selectivity. Remarkably, this proceeded one carbon–carbon double bond allenes, which regioselective complementary the Rh-catalyzed asymmetric version. Deuterium labeling experiments density functional theory (DFT) calculations were carried out reveal reasonable reaction mechanism explain regio-/stereoselectivity.

Language: Английский

---

Photocatalysis Meets Copper Catalysis: A New Opportunity for Asymmetric Multicomponent Radical Cross-Coupling Reactions

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 13, 2024

ConspectusIn recent years, radical-mediated cross-coupling reactions have emerged as a compelling strategy for achieving rich diversity in molecular topologies under benign conditions. However, the inherent high reactivity of radicals presents considerable challenges controlling reaction pathways and selectivity, which often results limited range substrates constrained profile. Given capacity visible-light photoredox catalysis to generate wide variety reactive radical ions controlled manner propensity copper complexes toward species, we envisaged that synergy between chiral catalysts photoactive would pave way developing innovative strategies. This integration is poised unlock broad spectrum enantioselective multicomponent reactions.In this Account, describe our insights efforts realm reactions. These advancements been achieved through application dual photoredox/copper or bifunctional visible light irradiation. Our work systematically divided into two sections based on activation modes. The first section focuses photoinduced copper-catalyzed C-C C-O bond formation addition/nucleophilic trap sequence. discussion particularly concentrated asymmetric carbocyanation carboarylation vinylarenes, 1,3-enynes, 1,3-dienes. findings underscore irradiation with can adeptly modulate pace generation, thus orchestrating consecutive stages ensuring attainment both chemo- stereoselectivity. In domain formation, leveraging carboxylic acids nucleophilic oxygen source, introduce suite esterification benzylic, allylic, propargylic radicals. are derived from precursors, showcasing versatility approach. following highlights discovery field catalysis, enables three-component transformations via direct aromatic alkenes. methodology begins generation formal distonic anions photocatalytic single-electron reduction alkenes, thus, enabling orthogonal reactivity. Employing H

Language: Английский

---

Visible-Light-Induced Regioselective Radical-Polar Crossover 1,4-Hydrophosphinylation of 1,3-Enynes: Access to Trisubstituted Allenes Bearing a Phosphine Oxide Group

Organic Letters, Journal Year: 2024, Volume and Issue: 26(22), P. 4678 - 4683

Published: May 24, 2024

The radical 1,4-functionalizations of 1,3-enynes have emerged as a powerful strategy for the synthesis multisubstituted allenes. However, phosphorus-centered radical-initiated transformations remain largely elusive. Herein, visible-light photoredox catalytic regioselective hydrophosphinylation with diaryl phosphine oxides phosphinoyl precursors has been realized. This protocol features mild conditions, wide substrate scope, and good functional group tolerance, producing diverse range phosphinoyl-substituted allenes in moderate to yields high atom economy. Detailed mechanistic experiments revealed radical-polar crossover process reaction.

Language: Английский

---

Copper-Initiated Regiodivergent Chloropentafluorosulfanylation of 1,3-Enynes under Substrate Control

Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 5049 - 5054

Published: June 4, 2024

A copper-catalyzed regiodivergent chloropentafluorosulfanylation strategy for 1,3-enynes using SF

Language: Английский

---

Photoinduced copper-catalyzed asymmetric radical three-component cross-coupling of 1,3-enynes with oxime esters and carboxylic acids

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(11), P. 2773 - 2781

Published: Jan. 1, 2023

A regio- and enantioselective radical three-component coupling of 1,3-enynes, oxime esters, carboxylic acids through photoinduced copper catalysis is reported.

Language: Английский

---

Synthesis of Trifluoromethyl-Substituted Allenols via Catalytic Trifluoromethylbenzoxylation of 1,3-Enynes

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(3), P. 2142 - 2148

Published: Jan. 25, 2023

Allenol has been identified as a versatile building block for organic synthesis, and numerous efforts have made to synthesize apply allenol. However, limited obtain trifluoromethyl-substituted Here, by using readily available 1,3-enyne the starting material, copper-catalyzed trifluoromethylbenzoxylation process was developed efficient synthesis of allenols Togni-II reagent reaction partner. Triple roles reagent, including source trifluoromethyl group, hydroxyl oxidant, were elucidated in this transformation. Moreover, late-stage diversification performed, which revealed application potential preparation various compounds.

Language: Английский

---