puc-header

B(C 6F 5) 3-Catalyzed C(Sp 3)-F Bond Activation With/Without the Cooperation of HFIP: Synthesis of Spirobiindanes, Monofluoroalkenes, and Indane Derivatives

181 Pages Posted: 19 May 2019 Sneak Peek Status: Published

See all articles by Jiandong Wang

Jiandong Wang

Nagoya Institute of Technology - Department of Nanopharmaceutical Sciences; Nagoya Institute of Technology - Department of Life Science and Applied Chemistry

Yuta Ogawa

Nagoya Institute of Technology - Department of Nanopharmaceutical Sciences; Nagoya Institute of Technology - Department of Life Science and Applied Chemistry

Norio Shibata

Nagoya Institute of Technology - Department of Nanopharmaceutical Sciences; Nagoya Institute of Technology - Department of Life Science and Applied Chemistry; Zhejiang Normal University - Institute of Advanced Fluorine-Containing Materials

More...

Abstract

The activation of C(sp3)-F bond in saturated fluorocarbons, especially for aliphatic gem-difluoroalkanes, remains challenging and less reported. Herein, we describe the selective activation of inert C(sp3)-F bonds catalyzed by B(C6F5)3. In hexafluoro-2-propanol (HFIP), chemically robust aliphatic gem-difluorides are converted in high yields to the corresponding substituted 2,2',3,3'-tetrahydro-1,1'-spirobiindenes via a B(C6F5)3-catalyzed intramolecular cascade Friedel-Crafts cyclization, whereby a silicon-based trapping reagent is not required. However, in the absence of a hydrogen-bonding donor solvent such as HFIP, the aliphatic gem-difluorides preferentially engage in a defluorination/elimination process that provides monofluorinated alkenes in good yields. In addition, a series of substituted 1-alkyl-2,3-dihydro-1H-indenes was obtained in high yield from the B(C6F5)3-catalyzed defluorinative cyclization of aliphatic secondary monofluorides in HFIP. The protocol could inspire the development of a new class of main-group Lewis acids-catalyzed C(sp3)-F bond activation in general unactivated fluorocarbons.

Keywords: fluorine, C-F bond activation, Cyclization, catalysis, spiro compounds, fluorro-olefine

Suggested Citation

Wang, Jiandong and Ogawa, Yuta and Shibata, Norio, B(C 6F 5) 3-Catalyzed C(Sp 3)-F Bond Activation With/Without the Cooperation of HFIP: Synthesis of Spirobiindanes, Monofluoroalkenes, and Indane Derivatives (May 17, 2019). ISCIENCE-D-19-00359. Available at SSRN: https://ssrn.com/abstract=3389886 or http://dx.doi.org/10.2139/ssrn.3389886
This is a paper under consideration at Cell Press and has not been peer-reviewed.

Jiandong Wang

Nagoya Institute of Technology - Department of Nanopharmaceutical Sciences

Nagoya
Japan

Nagoya Institute of Technology - Department of Life Science and Applied Chemistry

Nagoya
Japan

Yuta Ogawa

Nagoya Institute of Technology - Department of Nanopharmaceutical Sciences ( email )

Nagoya
Japan

Nagoya Institute of Technology - Department of Life Science and Applied Chemistry ( email )

Nagoya
Japan

Norio Shibata (Contact Author)

Nagoya Institute of Technology - Department of Nanopharmaceutical Sciences ( email )

Nagoya
Japan

Nagoya Institute of Technology - Department of Life Science and Applied Chemistry ( email )

Nagoya
Japan

Zhejiang Normal University - Institute of Advanced Fluorine-Containing Materials ( email )

Jinhua
China

Click here to go to Cell.com

Go to Cell.com

Paper statistics

Abstract Views
273
Downloads
8