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Selective Synthesis of Spirobiindanes, Alkenyl Chlorides, and Monofluoroalkenes from Unactivated Gem-Difluoroalkanes Controlled by Aluminum-Based Lewis Acids

84 Pages Posted: 26 Jul 2019 Sneak Peek Status: Review Complete

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

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Abstract

The highly selective synthesis of spirobiindanes, alkenyl chlorides, and monofluoroalkenes via the cleavage of inert C(sp3)-F bonds in unactivated gem-difluoroalkanes using readily available and inexpensive aluminum-based Lewis acids of low toxicity is reported. The selectivity of this reaction can be controlled by modifying the substituents on the central aluminum atom of the promoter. An intramolecular cascade Friedel-Crafts alkylation of unactivated gem-difluorocarbons can be achieved using a stoichiometric amount of AlCl3. The subsequent synthesis of alkenyl chlorides via F/Cl exchange followed by an elimination can be accomplished using AlEt2Cl as a fluoride scavenger and halogen source. The defluorinative elimination of acyclic and cyclic gem-difluorocarbons to give monofluoroalkenes can be achieved using AlEt3.

Keywords: fluorine, aluminum, C-F bond activation, spiro, fluoroalkenes, alkenyl chlorides

Suggested Citation

Wang, Jiandong and Ogawa, Yuta and Shibata, Norio, Selective Synthesis of Spirobiindanes, Alkenyl Chlorides, and Monofluoroalkenes from Unactivated Gem-Difluoroalkanes Controlled by Aluminum-Based Lewis Acids (July 25, 2019). ISCIENCE-D-19-00716. Available at SSRN: https://ssrn.com/abstract=3426653 or http://dx.doi.org/10.2139/ssrn.3426653
This is a paper under consideration at Cell Press and has not been peer-reviewed.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

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