Synthetic Utilization of 2H-Heptafluoropropane: Ionic 1,4-Addition to Electron-Deficient Carbon–Carbon Unsaturated Bonds DOI Creative Commons
Y. Higashi,

Kotono Shima,

Mikiya Suzuki

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(6), P. 3962 - 3969

Published: March 5, 2024

We have found a novel method for introducing heptafluoro-2-propyl CF(CF3)2 groups into carbon–carbon unsaturated bonds via nucleophilic reaction using 2H-heptafluoropropane as the source of groups. The involves addition anion, generated by treating with fluoride ion, to various electron-deficient compounds. This allows easy synthesis aliphatic compounds containing

Language: Английский

Photo-induced hydroxypentafluorosulfanylation of alkenes with SF5Cl and oxygen gas and their further derivatization DOI Creative Commons
Y. Jiang,

Xiao-Li Meng,

Jiangshan Zhang

et al.

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

Published: Nov. 9, 2024

Fluorinated or fluoroalkylated alcohols are common structural motifs in biologically active molecules, natural products, and pharmaceuticals. However, pentafluorosulfanyl (SF

Language: Английский

Citations

6
Perfluoroalkylation Reactions by Electron Donor‐Acceptor Complexes: Recent Advances DOI
Damian E. Yerien, Sebastián Barata‐Vallejo, Al Postigo

et al.

ChemPhotoChem, Journal Year: 2024, Volume and Issue: 8(8)

Published: May 3, 2024

Abstract This Perspective analyses the perfluoroalkylation reactions by electron donor‐acceptor (EDA) complexes since 2018, while summarizes, in Tables , vast majority of representative various classes organic compounds EDA and halogen‐bonding interactions. Numerous intriguing reaction methodologies valuable synthetic instances have emerged. We aim to delve into these new examples comprehensively, also contemplating future directions field. Subsequent sections will elaborate on (hetero)aromatic compounds, carbon‐carbon multiple bonds, carbonyl isocyanides, covering their scope mechanistic insights. Perfluoroalkylation complexes. Entry Substrate Complex Reaction conditions Product Ref. 1 [13] 2 [46] 3 R F I (3 equiv.) KOH (1.5 Blue LEDs H O, Ar, 20 h [47] 4 TEEDA CFL (25 W) THF, r.t. F− [48] 5 ICF CO Et (1.3 Na DMSO mL) rt. 427 nm LED, 16 [49] 6 TMG (2.5 23 W CFL, MeCN/Hex f (5 : 1) [42,50] 7 MeCN [51] 8 Umemoto's reagent (2 N ‐methylmorpholine DMF, [52] 9 Cs white light O r.t., [53] 10 4.5 450 laser CaCl MeNO 0 °C [3] 11 t ‐BuONa DMF Green [54] 12 or complex I−R (2.1 TMEDA DBU 24 [55,56] 13 TFE/water (1 (0.2 M) CF SO [84] bonds constrained cyclic Bu NCl, Hg lamp (6 (1.2 CH OH, 1.5 r.t, Ar [39] [57] DIPEA …….. −I Base THF 25 with DIPEA, TEEDA; [48,58,59] Bn NH [60] Base, [61] O/toluene=9 LEDs, 65 °C, [41] K PO CuCl (10 mol%) TMSNCS CN Violet (24 [37] Diphenylacetaldehyde Pyrrolidine (40 DCE mL); (0.8 eq.); White W); [44,62] DIPEA,DMA (trace air) 36–72 [63] n ‐C air, RT [64] DABCO υ (400 Watt) 50 C 2n+1 (1.8 [65–67] DCE, [27] 14 2,4,6‐trimethylpyridine MeCN, 60 Togni's [68] 15 PMDETA [69] [70,71] 17 less than % water mmol) isocyanides hydrazones. [72,73] cis ‐catalyst M (20 2,6‐lutidine (0.7 ‐10 [74] [75] phase transfer catalyst Cl/8F 18 1), [32] ambient NaOH (4.1 R.T. [76] 36 30 [77] I−C [78] [79] Imidazole [80]

Language: Английский

Citations

4
10-Phenylphenothiazine-Organophotocatalyzed Bromo-Perfluoroalkylation of Unactivated Olefins DOI
Koto Tagami,

Moeko Nakayama,

Tadashi Kanbara

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(10), P. 7084 - 7094

Published: April 25, 2024

In this study, we have developed a smooth metal-free visible-light-induced bromo-perfluoroalkylation of unactivated olefins with the aid 10-phenylphenothiazine (PTH) as an organic photoredox catalyst. The reaction is 100% atom-economic redox-neutral and proceeds stoichiometric amounts olefin perfluoroalkyl bromide. To show potential these unexplored motifs, carried out various postfunctionalizations taking advantage bromine atom, including gram-scale experiments.

Language: Английский

Citations

2
TBHP‐Mediated Hydroxyperfluoroalkylation of Alkenes with Perfluoroalkyl Iodides to Construct β‐Perfluoroalkyl Alcohols DOI
Jiantao Zhang, Weiming Zhu,

Renhua Su

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(17), P. 3572 - 3577

Published: April 10, 2024

Abstract A three‐component strategy for the synthesis of β‐perfluoroalkyl allyl alcohols from 1,3‐dienes is developed. diverse range synthetically valuable are obtained in moderate to high yields. Broad substrate scope and good functional group tolerance observed. This method also applicable mono‐olefins 1,3‐enynes. The control experiment results demonstrate that hydroxyl OH product comes TBHP. In addition, practicality mild reaction conditions make these synthetic transformations attractive organic synthesis.

Language: Английский

Citations

1
Bayesian optimization assisted screening conditions for visible light-induced hydroxy-perfluoroalkylation DOI Creative Commons
Koto Tagami, Masaru Kondo, Shinobu Takizawa

et al.

Journal of Fluorine Chemistry, Journal Year: 2024, Volume and Issue: 276, P. 110294 - 110294

Published: May 1, 2024

The reaction conditions for the visible light-induced hydroxy-perfluoroalkylation of olefins were explored using Bayesian optimization (BO). This is first application BO to photoreaction synthesis fluorinated compounds. Five parameters, including light irradiation intensity, simultaneously examined, thereby enabling investigation minimal experimentation. key parameters identified by calculating correlation coefficients each parameter. Furthermore, individual achieved different and perfluoroalkyl bromides.

Language: Английский

Citations

1
TMSCN-Promoted Difunctionalization of Alkenes for the Synthesis of Alcohol Derivatives DOI
Jiantao Zhang,

Renhua Su,

Weiming Zhu

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(17), P. 12062 - 12070

Published: Aug. 15, 2024

A TMSCN-promoted difunctionalization of styrenes with CHCl3 and TBHP is reported via the radical addition/cross coupling process. wide range dichloromethyl-substituted alcohol derivatives were synthesized under transition-metal-free conditions. Besides, this method also applicable to unactive alkenes. The key success lies in role TMSCN, which prevents reaction toward dichloromethylperoxylation olefins. This represents an alternative approach for synthesizing diverse using readily available substrates, holding significant promise fields pharmaceutical chemistry natural product synthesis.

Language: Английский

Citations

1
Hydroxy- and Hydro-Perfluoroalkylation of Styrenes by Controlling the Quenching Cycle of Eosin Y DOI Creative Commons

Haruko Shibata,

Moeko Nakayama,

Koto Tagami

et al.

Molecules, Journal Year: 2023, Volume and Issue: 28(22), P. 7577 - 7577

Published: Nov. 14, 2023

Fluoroalkyl compounds are widely used, underscoring a pressing need for the development of methods their synthesis. However, reports on perfluoroalkylation to styrenes have been sparse. In this study, both hydroxy- and hydro-perfluoroalkylation styrene were achieved using visible light reactions, catalyzed by eosin Y, selecting appropriate additives controlling Y quenching cycle. These reactions heavy-metal free, use water as hydroxyl or hydrogen source, employ inexpensive readily available reagents.

Language: Английский

Citations

3
Synthetic Utilization of 2H-Heptafluoropropane: Ionic 1,4-Addition to Electron-Deficient Carbon–Carbon Unsaturated Bonds DOI Creative Commons
Y. Higashi,

Kotono Shima,

Mikiya Suzuki

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(6), P. 3962 - 3969

Published: March 5, 2024

We have found a novel method for introducing heptafluoro-2-propyl CF(CF3)2 groups into carbon–carbon unsaturated bonds via nucleophilic reaction using 2H-heptafluoropropane as the source of groups. The involves addition anion, generated by treating with fluoride ion, to various electron-deficient compounds. This allows easy synthesis aliphatic compounds containing

Language: Английский

Citations

0