Rh(III)-Catalyzed Intra- and Intermolecular 3,4-Difunctionalization of 1,3-Dienes via Rh(III)-π-Allyl Amidation with 1,4,2-Dioxazolones DOI
Finn Burg, Tomislav Rovis

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(15), P. 9690 - 9697

Published: July 26, 2022

We herein report a modular strategy, which enables Rh(III)-catalyzed diastereoselective 3,4-amino oxygenation and diamination of 1,3-dienes using different O- N-nucleophiles in combination with readily available 3-substituted 1,4,2-dioxazolones (78 examples, 37–91% yield). Previous attempts to functionalize the internal double bond rested on use plain alcoholic solvents as nucleophilic coupling partners thus dramatically limiting scope this transformation. have now identified hexafluoroisopropanol non-nucleophilic solvent that allows diverse nucleophiles greatly expands scope, including an unprecedented amino hydroxylation selectively install valuable, unprotected β-amino alcohols across 1,3-dienes. Moreover, various elaborate prove be compatible providing unique access complex organic molecules. Finally, method is employed series intramolecular reactions deliver valuable nitrogen heterocycles well γ- δ-lactones.

Language: Английский

Diastereoselective Three-Component 3,4-Amino Oxygenation of 1,3-Dienes Catalyzed by a Cationic Heptamethylindenyl Rhodium(III) Complex DOI
Finn Burg, Tomislav Rovis

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(43), P. 17964 - 17969

Published: Oct. 20, 2021

The direct oxyamination of olefins is a compelling tool to rapidly access β-amino alcohols–a privileged motif ubiquitous in natural products, pharmaceuticals and agrochemicals. Although variety expedient methods are established for simple alkenes, selective amino oxygenation 1,3-dienes less explored. Within this context, the that internal position remain unprecedented. We herein report modular three-component approach perform an highly diastereoselective catalyzed by cationic heptamethylindenyl (Ind*) Rh(III) complex.

Language: Английский

Citations

33
Photoinduced Transition-Metal-Free Chan–Evans–Lam-Type Coupling: Dual Photoexcitation Mode with Halide Anion Effect DOI
Zijun Zhou, Jeonguk Kweon, Hoimin Jung

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(20), P. 9161 - 9171

Published: May 12, 2022

Herein, we report a photoinduced transition-metal-free C(aryl)-N bond formation between 2,4,6-tri(aryl)boroxines or arylboronic acids as an aryl source and 1,4,2-dioxazol-5-ones (dioxazolones) amide coupling partner. Chloride anion, either generated

Language: Английский

Citations

25
Cross‐Coupling of C−H and N−H Bonds: A Hydrogen Evolution Strategy for the Construction of C−N Bonds DOI

Ravindar Lekkala,

Siti Aishah Hasbullah, Nurul Izzaty Hassan

et al.

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 2022(31)

Published: July 22, 2022

Abstract The progress in C−N bond construction is significant synthetic and biological chemistry. Cross‐dehydrogenative couplings of C−H N−H motifs serve as a unique class the most atom‐economical straightforward strategies for constructing bonds. Herein, we enclosed updated methodologies developed assembly bonds via photo‐catalyzed, transition‐metal‐catalyzed, electrochemical, metal‐free amination amidation reactions saturated unsaturated Compared with well‐established transition‐metal‐catalyzed protocols, electricity, or visible light‐mediated are competent appealing. Plausible mechanistic pathways also described representative to provide insights future development environmentally kind processes.

Language: Английский

Citations

24
A Rh(III)-Catalyzed Formal [4+1] Approach to Pyrrolidines from Unactivated Terminal Alkenes and Nitrene Sources DOI
Sumin Lee, Honghui Lei, Tomislav Rovis

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(32), P. 12536 - 12540

Published: Aug. 5, 2019

We have developed a formal [4+1] approach to pyrrolidines from readily available unactivated terminal alkenes as 4-carbon partners. The reaction provides rapid construction of various pyrrolidine containing structures, especially for the diastereoselective synthesis spiro-pyrrolidines. Mechanistic investigation suggests Rh(III)-catalyzed intermolecular aziridination alkene and subsequent acid-promoted ring expansion formation.

Language: Английский

Citations

42
Rh(III)-Catalyzed Intra- and Intermolecular 3,4-Difunctionalization of 1,3-Dienes via Rh(III)-π-Allyl Amidation with 1,4,2-Dioxazolones DOI
Finn Burg, Tomislav Rovis

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(15), P. 9690 - 9697

Published: July 26, 2022

We herein report a modular strategy, which enables Rh(III)-catalyzed diastereoselective 3,4-amino oxygenation and diamination of 1,3-dienes using different O- N-nucleophiles in combination with readily available 3-substituted 1,4,2-dioxazolones (78 examples, 37–91% yield). Previous attempts to functionalize the internal double bond rested on use plain alcoholic solvents as nucleophilic coupling partners thus dramatically limiting scope this transformation. have now identified hexafluoroisopropanol non-nucleophilic solvent that allows diverse nucleophiles greatly expands scope, including an unprecedented amino hydroxylation selectively install valuable, unprotected β-amino alcohols across 1,3-dienes. Moreover, various elaborate prove be compatible providing unique access complex organic molecules. Finally, method is employed series intramolecular reactions deliver valuable nitrogen heterocycles well γ- δ-lactones.

Language: Английский

Citations

19