A photocatalyzed aliphatic fluorination

Bloom, Steven; Knippel, James Levi; Lectka, Thomas

doi:10.1039/c3sc53261e

Cited by 126 publications

(56 citation statements)

References 34 publications

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“…12 The Lectka group then published a copper and an iron catalyst system. 13 Subsequently, we disclosed a ketone-catalyzed photolytic method 14 and the Inoue group an N -oxyl radical-catalyzed method. 15 More recently, the Doyle group developed a palladium-catalyzed allylic C(sp 3 )–H fluorination reaction 16 and the Hartwig group a silver-promoted oxidative method for C(sp 2 )–H fluorination of heterocycles.…”

mentioning

confidence: 99%

Vanadium-catalyzed C(sp³)–H fluorination reactions

Xia

Chen

2014

Org. Chem. Front.

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mentioning

confidence: 99%

Vanadium-catalyzed C(sp³)–H fluorination reactions

Xia

Chen

2014

Org. Chem. Front.

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“…Our laboratory recently unveiled a photocatalyzed procedure for the monofluorination of aliphatic 1d and benzylic 1g substrates by using the inexpensive photosensitizer 1,2,4,5‐tetracyanobenzene (TCB) along with Selectfluor as a source of atomic fluorine 4. This work was accompanied by a number of alternative sp 3 CH fluorination methods by using photosensitizers, such as fluorenone, 2d acetophenone, 2f anthraquinone, 2h and decatungstate ions.…”

Section: Methodsmentioning

confidence: 99%

Site‐Selective Approach to β‐Fluorination: Photocatalyzed Ring Opening of Cyclopropanols

Bloom

Bume

Pitts

et al. 2015

Chemistry A European J

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107

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To expand upon the recent pioneering reports of catalyzed sp(3) C-H fluorination methods, the next rational step is to focus on directing "radical-based fluorination" more effectively. One potential solution entails selective C-C bond activation as a prelude to selective fluorination. Herein, we report the tandem photocatalyzed ring-opening/fluorination reactions of cyclopropanols by 1,2,4,5-tetracyanobenzene (TCB) and Selectfluor to afford a process tantamount to site-selective β-fluorination of carbonyl-containing compounds. This new approach provides a synthetically mild and operationally simple route to otherwise difficult-to-prepare β-fluorinated products in good yields and with good-to-excellent regioselectivity. Remarkably, substrates that contain other usually reactive (e.g., benzylic) sites undergo ring-opening fluorination preferably. The versatility of this method to give cyclic β-fluorides from tertiary cyclopropanols and γ-fluoro alcohols is also highlighted.

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“…It can be seen from Scheme 5 that the formation of Ru−Fcontaining ions [7] + and [7a] + is thermodynamically favored over 2 and [FTMP] + (by 158 and 208 kJ mol −1 , respectively). As such, the fact that a Ru−F species is not observed is likely to be a kinetic effect.…”

Section: Formation Of 5 From [4][bfmentioning

confidence: 98%

Outer-Sphere Electrophilic Fluorination of Organometallic Complexes

et al. 2015

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Organofluorine chemistry plays a key role in materials science, pharmaceuticals, agrochemicals, and medical imaging. However, the formation of new carbon-fluorine bonds with controlled regiochemistry and functional group tolerance is synthetically challenging. The use of metal complexes to promote fluorination reactions is of great current interest, but even state-of-the-art approaches are limited in their substrate scope, often require activated substrates, or do not allow access to desirable functionality, such as alkenyl C(sp(2))-F or chiral C(sp(3))-F centers. Here, we report the formation of new alkenyl and alkyl C-F bonds in the coordination sphere of ruthenium via an unprecedented outer-sphere electrophilic fluorination mechanism. The organometallic species involved are derived from nonactivated substrates (pyridine and terminal alkynes), and C-F bond formation occurs with full regio- and diastereoselectivity. The fluorinated ligands that are formed are retained at the metal, which allows subsequent metal-mediated reactivity.

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A photocatalyzed aliphatic fluorination

Abstract: We disclose a new approach to the catalysis of alkane fluorination employing ultraviolet light and a photosensitizer, 1,2,4,5-tetracyanobenzene (TCB).

Cited by 126 publications

References 34 publications

Vanadium-catalyzed C(sp³)–H fluorination reactions

Vanadium-catalyzed C(sp³)–H fluorination reactions

Site‐Selective Approach to β‐Fluorination: Photocatalyzed Ring Opening of Cyclopropanols

Outer-Sphere Electrophilic Fluorination of Organometallic Complexes

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A photocatalyzed aliphatic fluorination

Abstract: We disclose a new approach to the catalysis of alkane fluorination employing ultraviolet light and a photosensitizer, 1,2,4,5-tetracyanobenzene (TCB).

Cited by 126 publications

References 34 publications

Vanadium-catalyzed C(sp3)–H fluorination reactions

Vanadium-catalyzed C(sp3)–H fluorination reactions

Site‐Selective Approach to β‐Fluorination: Photocatalyzed Ring Opening of Cyclopropanols

Outer-Sphere Electrophilic Fluorination of Organometallic Complexes

Contact Info

Product

Resources

About

Vanadium-catalyzed C(sp³)–H fluorination reactions

Vanadium-catalyzed C(sp³)–H fluorination reactions