Azido-alkynylation of alkenes through radical-polar crossover

Chemical Science, Journal Year: 2023, Volume and Issue: 14(35), P. 9452 - 9460

Published: Jan. 1, 2023

We report an azido-alkynylation of alkenes allowing a straightforward access to homopropargylic azides by combining hypervalent iodine reagents and alkynyl-trifluoroborate salts. The design photocatalytic redox-neutral radical polar crossover process was key develop this transformation. A variety possessing electron-rich -poor aryls, heterocycles or ether substituents could be accessed in 34-84% yield. products are synthetically useful building blocks that easily transformed into pyrroles bioactive amines.

Language: Английский

---

B(C₆F₅)₃-Catalyzed C(sp³)–H Alkylation of Tertiary Amines with Electron-Deficient Olefins: Determinants of Site Selectivity

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(10), P. 8041 - 8049

Published: May 8, 2024

The reason for the site selectivity previously reported B(C6F5)3-catalyzed C(sp3)–H alkylation of tertiary amines with electron-deficient olefins remains a mystery. appears to be governed by number electron-withdrawing groups (EWGs) on olefin: one EWG results in α-alkylation, whereas two EWGs (one each end double bond) result β-alkylation. In this study, we solved mystery and unlocked pathway β-alkylation bearing only EWG. Control experiments density functional theory calculations provided detailed picture reaction mechanism both α- Furthermore, demonstrated broad scope reaction.

Language: Английский

---

Cu(II)-Catalyzed [3 + 1 + 1 + 1] Cyclization of 1,3-Diketones and 2-Naphthols Using N,N-Dimethylethanolamine as a Dual Carbon Synthon for the Synthesis of 2H-Chromenes

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 89(1), P. 152 - 162

Published: Dec. 12, 2023

Reactions with diverse C1 synthons to realize homologation were well explored. However, homologations occurring twice one synthon in a reaction less reported. We disclose herein Cu(II)-catalyzed novel and efficient synthesis of 2H-chromenes from 2-naphthols, 1,3-diketones, N,N-dimethylethanolamine (DMEA) as dual carbon synthon. Various different functional groups are constructed moderate good yields. This is the first report that DMEA acts

Language: Английский

---

Recent Advances in Catalysis Using Organoborane-Mediated Hydride Abstraction

Synlett, Journal Year: 2023, Volume and Issue: 34(18), P. 2117 - 2128

Published: June 16, 2023

Abstract C–H functionalization is widely regarded as an important area in the development of synthetic methodology, enabling design more time- and atom-efficient syntheses. The ability electron-deficient organoboranes to mediate hydride abstraction from α-amino bonds therefore great interest, reactive iminium hydridoborate moieties generated are able participate a range synthetically useful transformations. In this review, we cover recent advances made organoborane-mediated abstraction, focus on catalytic applications boranes α- or β-functionalization, α,β-difunctionalization, dehydrogenation amines. 1 Introduction 2 α-Functionalization Amines 3 β-Functionalization 4 α,β-Difunctionalization 5 Dehydrogenation 6 Summary Future Prospects

Language: Английский

---

B(C₆F₅)₃-catalyzed stepwise 1,5-hydride migration/cyclization: diastereoselective construction of carbocyclic β-amino acid derivatives

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 11(3), P. 864 - 870

Published: Dec. 11, 2023

A stepwise 1,5-hydride migration/cyclization reaction enabled by B(C 6 F 5 ) 3 is established to deliver the corresponding six-membered carbocyclic β-amino acid derivatives with complete diastereoselectivity.

Language: Английский

---

Quinoline as an Intramolecular Hydride Shuttle in the Deoxygenative Coupling Reaction of Alcohol and the Inert Methyl C(sp³)–H Bond

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 9, 2024

Reported herein is the C(sp

Language: Английский

---