The Fluorination of C-H Bonds: Developments and Perspectives

被引:352
作者
Szpera, Robert [1 ]
Moseley, Daniel F. J. [1 ]
Smith, Lewis B. [1 ]
Sterling, Alistair J. [1 ]
Gouverneur, Veronique [1 ]
机构
[1] Univ Oxford, Chem Res Lab, 12 Mansfield Rd, Oxford OX1 3TA, England
基金
英国工程与自然科学研究理事会;
关键词
C-H activation; fluorination; radical chemistry; radiochemistry; transition-metal catalysis; LATE-STAGE FLUORINATION; REDUCTIVE ELIMINATION; SELECTIVE FLUORINATION; AMINO-ACIDS; ENANTIOSELECTIVE EPOXIDATION; PHOTOCATALYTIC FLUORINATION; OXIDATIVE ACTIVATION; CATALYTIC METHOD; PALLADIUM; LIGHT;
D O I
10.1002/anie.201814457
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
This Review summarizes advances in fluorination by C(sp(2))-H and C(sp(3))-H activation. Transition-metal-catalyzed approaches championed by palladium have allowed the installation of a fluorine substituent at C(sp(2)) and C(sp(3)) sites, exploiting the reactivity of high-oxidation-state transition-metal fluoride complexes combined with the use of directing groups (some transient) to control site and stereoselectivity. The large majority of known methods employ electrophilic fluorination reagents, but methods combining a nucleophilic fluoride source with an oxidant have appeared. External ligands have proven to be effective for C(sp(3))-H fluorination directed by weakly coordinating auxiliaries, thereby enabling control over reactivity. Methods relying on the formation of radical intermediates are complementary to transition-metal-catalyzed processes as they allow for undirected C(sp(3))-H fluorination. To date, radical C-H fluorinations mainly employ electrophilic N-F fluorination reagents but a unique Mn-III-catalyzed oxidative C-H fluorination using fluoride has been developed. Overall, the field of late-stage nucleophilic C-H fluorination has progressed much more slowly, a state of play explaining why C-H F-18-fluorination is still in its infancy.
引用
收藏
页码:14824 / 14848
页数:25
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