Outer-Sphere Electrophilic Fluorination of Organometallic Complexes

TY - JOUR

T1 - Outer-Sphere Electrophilic Fluorination of Organometallic Complexes

AU - Milner, Lucy M.

AU - Pridmore, Natalie E.

AU - Whitwood, Adrian C.

AU - Lynam, Jason M.

AU - Slattery, John M.

PY - 2015/8/26

Y1 - 2015/8/26

N2 - 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(sp2)-F or chiral C(sp3)-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.

AB - 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(sp2)-F or chiral C(sp3)-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.

UR - http://www.scopus.com/inward/record.url?scp=84940862762&partnerID=8YFLogxK

U2 - 10.1021/jacs.5b06547

DO - 10.1021/jacs.5b06547

M3 - Article

AN - SCOPUS:84940862762

SN - 0002-7863

VL - 137

SP - 10753

EP - 10759

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 33

ER -