Photoredox Radical Truce–Smiles Rearrangement of N-Sulfinyl Acrylamides with Bromodifluoroacetamides DOI
Lin Tian, Pu Chen, Xiaochen Ji

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 18, 2024

We herein report a photochemical Truce–Smiles rearrangement reaction of N-sulfinyl acrylamides with bromodifluoroacetamides resulting in the synthesis series aryl difluoroglutaramides moderate to good yields. The asymmetric using chiral sulfinamides produced quaternary carbon-centered glutaramide products modest enantioselectivity. This protocol effectively complements previous methods involving N-sulfonyl acrylamides.

Language: Английский

A Journey of the Development of Privileged Difluorocarbene Reagents TMSCF2X (X = Br, F, Cl) for Organic Synthesis DOI
Qiqiang Xie, Jinbo Hu

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(5), P. 693 - 713

Published: Feb. 14, 2024

ConspectusAs fluorine has played an increasingly important role in modulating the physical, chemical, and biological properties of organic molecules, selective introduction atom(s) or fluorinated moieties into target molecules become a powerful tool development new pharmaceuticals, agrochemicals, functional materials. In this context, difluoromethylene (CF2) difluoromethyl (CF2H) groups are special interest because their ability to serve as bioisosteres ethereal oxygen atoms hydroxyl (OH) thiol (SH) groups, respectively. Difluorocarbene is one most versatile reactive intermediates incorporate CF2 CF2H groups; however, before 2006, previously known difluorocarbene reagents suffered from several drawbacks such using ozone-depleting substances (ODSs), difficult-to-handle reagents, harsh reaction conditions having narrow substrate scope and/or low yields. Moreover, reactivity generated different precursors (reagents) was often unpredictable, since generation (activation modes) various different, these may mismatch those required for subsequent difluorocarbene-involved transformations. Therefore, environmentally friendly well investigation mechanistic insights reactions, been highly desirable.In Account, we summarize our contributions applications synthesis 2006. We have developed seven including 2-chloro-2,2-difluoroacetophenone (1), chlorodifluoromethyl phenyl sulfone (2), S-difluoromethyl-S-phenyl-N-tosylsulfoximine (3), difluoromethyltri(n-butyl)ammonium chloride (4), (chlorodifluoromethyl)trimethylsilane (TMSCF2Cl, 5), (bromodifluoromethyl)trimethylsilane (TMSCF2Br, 6), (trifluoromethyl)trimethylsilane (TMSCF3, 7). journey, realized key factor ideal reagent that can be used broad range is, should allow activation modes species, under basic/acidic/neutral conditions, at wide temperatures, solvents, which compatible with Among all silanes TMSCF2X (X = Br, F, Cl) stood out privileged ones, paves avenue further developing chemistry. particular, TMSCF2Br recognized "all-rounder": applied almost common more importantly, also enables many other novel transformations cannot achieve, thanks its unique structure rich releasing conditions. It expected commercial availability now, chemistry will accelerated years come.

Language: Английский

Citations

21
Three-component approach to modular synthesis of tetra-substituted furans and pyrroles DOI
Pei Zhang,

Wenqing Ti,

Tianfeng Gao

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(9), P. 2554 - 2560

Published: Jan. 1, 2024

A three-component one-pot reaction of TMSCF 2 Br, p -QMs and 1,3-dicarbonyl compounds derivatives was developed. series densely functionalized tetra-substituted furans pyrroles were constructed with excellent chemoselectivities.

Language: Английский

Citations

1
Palladium-catalyzed difluorocarbene transfer enables access to enantioenriched chiral spirooxindoles DOI Creative Commons
Zhiwen Nie,

Keqin Wu,

Xiaohang Zhan

et al.

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

Published: Oct. 1, 2024

Language: Английский

Citations

1
Photoredox Radical Truce–Smiles Rearrangement of N-Sulfinyl Acrylamides with Bromodifluoroacetamides DOI
Lin Tian, Pu Chen, Xiaochen Ji

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 18, 2024

We herein report a photochemical Truce–Smiles rearrangement reaction of N-sulfinyl acrylamides with bromodifluoroacetamides resulting in the synthesis series aryl difluoroglutaramides moderate to good yields. The asymmetric using chiral sulfinamides produced quaternary carbon-centered glutaramide products modest enantioselectivity. This protocol effectively complements previous methods involving N-sulfonyl acrylamides.

Language: Английский

Citations

0