Simple Sulfinate Synthesis Enables CH Trifluoromethylcyclopropanation†
Ryan Gianatassio
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)
Search for more papers by this authorDr. Shuhei Kawamura
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)
Search for more papers by this authorCecil L Eprile
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)
Search for more papers by this authorDr. Klement Foo
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)
Search for more papers by this authorJason Ge
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)
Search for more papers by this authorDr. Aaron C. Burns
Department of Chemistry, Pfizer Pharmaceuticals, La Jolla Laboratories, 10770 Science Center Drive, La Jolla, CA 92121 (USA)
Search for more papers by this authorDr. Michael R. Collins
Department of Chemistry, Pfizer Pharmaceuticals, La Jolla Laboratories, 10770 Science Center Drive, La Jolla, CA 92121 (USA)
Search for more papers by this authorCorresponding Author
Prof. Dr. Phil S. Baran
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)Search for more papers by this authorRyan Gianatassio
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)
Search for more papers by this authorDr. Shuhei Kawamura
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)
Search for more papers by this authorCecil L Eprile
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)
Search for more papers by this authorDr. Klement Foo
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)
Search for more papers by this authorJason Ge
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)
Search for more papers by this authorDr. Aaron C. Burns
Department of Chemistry, Pfizer Pharmaceuticals, La Jolla Laboratories, 10770 Science Center Drive, La Jolla, CA 92121 (USA)
Search for more papers by this authorDr. Michael R. Collins
Department of Chemistry, Pfizer Pharmaceuticals, La Jolla Laboratories, 10770 Science Center Drive, La Jolla, CA 92121 (USA)
Search for more papers by this authorCorresponding Author
Prof. Dr. Phil S. Baran
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037 (USA)Search for more papers by this authorFinancial support for this work was provided by the NIH/NIGMS (GM-106210), Sigma–Aldrich, Inc., Pfizer, Inc., Uehara Memorial Foundation (postdoctoral fellowship for S.K.), and A*STAR (predoctoral fellowship for K.F.). We are grateful to Prof. A. L. Rheingold and Dr. C. E. Moore (UCSD) for X-ray crystallographic analysis, Dr. D.-H. Huang and Dr. L. Pasternack for assistance with NMR spectroscopy, and M. A. Ornelas for technical assistance.
Graphical Abstract
An interrupted Barton decarboxylation reaction has been used to convert readily available carboxylic acids into sulfinate salts (see scheme). Ten new sulfinate reagents were created and the reactivity of six of them towards CH functionalization was tested on a range of heterocycles. The simplicity of this approach (a cheap industrial oxidant, simple solvent, and no metals) is a clear advantage over other radical donors.
Abstract
A simple method to convert readily available carboxylic acids into sulfinate salts by employing an interrupted Barton decarboxylation reaction is reported. A medicinally oriented panel of ten new sulfinate reagents was created using this method, including a key trifluoromethylcyclopropanation reagent, TFCS-Na. The reactivity of six of these salts towards CH functionalization was field-tested using several different classes of heterocycles.
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