Organothianthrenium salts: synthesis and utilization

Chemical Science, Journal Year: 2022, Volume and Issue: 13(46), P. 13690 - 13707

Published: Jan. 1, 2022

This review summarizes the synthesis of diverse organothianthrenium salts from various precursors and their applications in organic to forge new C–C, C–H C–heteroatom bonds by C–S bond cleavage with different mechanistic considerations.

Language: Английский

---

Unified metal-free intermolecular Heck-type sulfonylation, cyanation, amination, amidation of alkenes by thianthrenation

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Jan. 15, 2024

Abstract Direct and site-selective C-H functionalization of alkenes under environmentally benign conditions represents a useful attractive yet challenging transformation to access value-added molecules. Herein, unified protocol for variety intermolecular Heck-type functionalizations C sp2 -H bond has been developed by thianthrenation. The reaction features metal-free operationally simple exclusive cine -selective aliphatic aryl forge C-C, C-N, C-P, C-S bonds at room temperature, providing general with nucleophiles (Nu = sulfinates, cyanides, amines, amides). Alkenes undergo -sulfonylation, cyanation, amination afford alkenyl sulfones, nitriles enamines.

Language: Английский

---

Regiospecific Alkene Aminofunctionalization via an Electrogenerated Dielectrophile

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8299 - 8307

Published: April 6, 2023

Modular strategies to rapidly increase molecular complexity have proven immensely synthetically valuable. In principle, transformation of an alkene into a dielectrophile presents opportunity deliver two unique nucleophiles across alkene. Unfortunately, the selectivity profiles known dielectrophiles largely precluded this deceptively simple synthetic approach. Herein, we demonstrate that dicationic adducts generated through electrolysis alkenes and thianthrene possess profile relative more conventional dielectrophiles. Specifically, these species undergo single perfectly regioselective substitution reaction with phthalimide salts. This observation unlocks appealing new platform for aminofunctionalization reactions. As illustrative example, implement reactivity paradigm address longstanding challenge: diamination distinct nitrogen nucleophiles. Studies mechanism process reveal key alkenyl thianthrenium salt intermediate controls exquisite regioselectivity highlight importance proton sources in controlling sulfonium electrophiles.

Language: Английский

---

Alkene Thianthrenation Unlocks Diverse Cation Synthons: Recent Progress and New Opportunities

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(16)

Published: Feb. 8, 2024

Oxidative alkene functionalization reactions are a fundamental class of complexity-building organic transformations. However, the majority established approaches rely on electrophilic reagents that limit diversity groups can be installed. Recent advances have new approach instead relies transformation alkenes into thianthrene-derived cationic electrophiles. These linchpin intermediates generated selectively and undergo diverse array mechanistically distinct with abundant nucleophiles. Taken together, this unlocks suite net oxidative transformations been elusive using conventional strategies. This Minireview describes these is organized around three synthons formally accessible from via thianthrenation: 1) alkenyl cations; 2) vicinal dications; 3) allyl cations. Throughout Minireview, we illustrate how thianthrenium salts address key limitations endemic to classic alkene-derived electrophiles highlight mechanistic origins distinctions wherever possible.

Language: Английский

---

Palladium-catalyzed regio- and stereo-selective phosphination of cyclic biarylsulfonium salts to access atropoisomeric phosphines

Chemical Science, Journal Year: 2024, Volume and Issue: 15(18), P. 6943 - 6948

Published: Jan. 1, 2024

A Pd-catalyzed atroposelective phosphination of cyclic biarylsulfonium salts with HPAr 3 Ar 4 for straightforward synthesis chiral phosphines bearing a stereogenic axis or both and P-stereogenic center is reported.

Language: Английский

---

Vinylic C–H Activation of Styrenes by an Iron–Aluminum Complex

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 4252 - 4259

Published: Feb. 2, 2024

The oxidative addition of sp2 C–H bonds alkenes to single-site transition-metal complexes is complicated by the competing π-coordination C═C double bond, limiting examples this type reactivity and onward applications. Here, we report activation styrenes a well-defined bimetallic Fe–Al complex. These reactions are highly selective, resulting in (E)-β-metalation alkene. For system, alkene binding appears be essential for reaction occur. Experimental computational insights suggest an unusual pathway which (2 + 2) cycloaddition intermediate directly converted into hydrido vinyl product via intramolecular bond across two metals. key cleavage step proceeds through asynchronous transition state near boundary between concerted stepwise mechanism influenced resonance stabilization ability aryl substituent. metalated can further functionalized, has been demonstrated (E)-selective phosphination employed styrenes.

Language: Английский

---

Organohypervalent heterocycles

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4786 - 4827

Published: Jan. 1, 2024

This review summarizes structural and synthetic aspects of heterocyclic molecules incorporating an atom a hypervalent main-group element. The higher thermal stability heterocycles, as compared to their acyclic analogs, adds special feature chemistry.

Language: Английский

---

Rhodium‐Catalyzed Divergent Arylation of Alkenylsulfonium Salts with Arylboroxines

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(49)

Published: Oct. 13, 2022

A ligand-controlled rhodium-catalyzed regiodivergent arylation of alkenylthianthrenium salts with arylboroxines which allows the synthesis terminal and internal alkene products in a switchable manner is reported. The use diene ligand guides reaction toward cine-arylation affording alkenes, while phosphine switches to ipso-arylation exclusively giving alkenes. Deuterium labelling studies DFT computations were carried out investigate mechanism.

Language: Английский

---

Highly Regioselective Dichalcogenation of Alkenyl Sulfonium Salts to Access 1,1-Dichalcogenalkenes

Organic Letters, Journal Year: 2023, Volume and Issue: 25(28), P. 5324 - 5328

Published: July 7, 2023

An unprecedented geminal olefinic dichalcogenation of alkenyl sulfonium salts with dichalcogenides ArYYAr (Y = S, Se, Te) is reported, providing various trisubstituted 1,1-dichalcogenalkenes [Ar1CH C(YAr2)2] in a highly selective manner under mild and catalyst-free conditions. The key process involves the formation two C-Y bonds via sequential cross-coupling C-H chalcogenation. A mechanistic rationale further supported by control experiments density functional theory calculations.

Language: Английский

---

Dithiolation of Alkenyl Sulfonium Salts with Arylthiols to Access 1,2-Dithioalkanes

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(22), P. 15767 - 15771

Published: Nov. 3, 2023

A dithiolation of alkenyl sulfonium salts with arylthiols is described, affording a series 1,2-dithioalkanes in high yields. This protocol features mild and catalyst-free conditions involves the formation two C–S bonds sequentially via regioselective addition an arylthiol to unsaturated C═C bonds, followed by attack another form exclusively.

Language: Английский

---