Issue in Honor of Prof. Kenneth K. Laali

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Supplementary Material
Metal-free synthesis of α,α-difluorocyclopentanone derivatives via
regioselective difluorocyclopropanation/VCP rearrangement of silyl dienol ethers
Ryo Takayama, Kohei Fuchibe, Junji Ichikawa*
Division of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba,Tsukuba, Ibaraki 305–8571, Japan
Email: junji@chem.tsukuba.ac.jp

Table of Contents
Figure S1. 1H NMR spectrum of cyclopentenyl silyl ether 3e (400 MHz, CDCl3)
Figure S2. 13C NMR spectrum of cyclopentenyl silyl ether 3e (100 MHz, CDCl3)
Figure S3. 19F NMR spectrum of cyclopentenyl silyl ether 3e (376 MHz, CDCl3)
Figure S4. 1H NMR spectrum of cyclopentenyl silyl ether 6g (500 MHz, CDCl3)
Figure S5. 13C NMR spectrum of cyclopentenyl silyl ether 6g (126 MHz, CDCl3)
Figure S6. 19F NMR spectrum of cyclopentenyl silyl ether 6g (470 MHz, CDCl3)
Figure S7. 1H NMR spectrum of cyclopentenyl silyl ether 3i and siloxydiene 7i (400 MHz, CDCl3)
Figure S8. 13C NMR spectrum of cyclopentenyl silyl ether 3i and siloxydiene 7i (126 MHz, CDCl3)
Figure S9. 19F NMR spectrum of cyclopentenyl silyl ether 3i and siloxydiene 7i (376 MHz, CDCl3)
Figure S10. NOE spectrum I of cyclopentenyl silyl ether 3i (400 MHz, CDCl3)
Figure S11. NOE spectrum II of cyclopentenyl silyl ether 3i (400 MHz, CDCl3)
Figure S12. 1H NMR spectrum of cyclopentenyl silyl ether 3j and siloxydiene 7j (400 MHz, CDCl3)
Figure S13. 13C NMR spectrum of cyclopentenyl silyl ether 3j and siloxydiene 7j (100 MHz, CDCl3)
Figure S14. 19F NMR spectrum of cyclopentenyl silyl ether 3j and siloxydiene 7j (376 MHz, CDCl3)

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Figure S1. 1H NMR of 1-[tert-Butyl(dimethyl)silyloxy]-5,5-difluoro-3-(4-trifluoromethylphenyl)cyclopent-1-ene (3e).

1H NMR of 1-[tert-Butyl(dimethyl)silyloxy]-5,5-difluoro-3-(4-trifluoromethylphenyl)cyclopent-1-ene (3e)Page S2©

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Figure S2. 13C NMR of 1-[tert-Butyl(dimethyl)silyloxy]-5,5-difluoro-3-(4-trifluoromethylphenyl)cyclopent-1-ene (3e).

13C NMR of 1-[tert-Butyl(dimethyl)silyloxy]-5,5-difluoro-3-(4-trifluoromethylphenyl)cyclopent-1-ene (3e)Page S3©

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Figure S3. 19F NMR of 1-[tert-Butyl(dimethyl)silyloxy]-5,5-difluoro-3-(4-trifluoromethylphenyl)cyclopent-1-ene (3e).

19F NMR of 1-[tert-Butyl(dimethyl)silyloxy]-5,5-difluoro-3-(4-trifluoromethylphenyl)cyclopent-1-ene (3e)Page S4©

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Figure S4. 1H NMR of 2-Bromo-1-[tert-butyl(dimethyl)silyloxy]-4,4-difluoro-3-phenylcyclopent-1-ene (6g).

1H NMR of 2-Bromo-1-[tert-butyl(dimethyl)silyloxy]-4,4-difluoro-3-phenylcyclopent-1-ene (6g)

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Figure S5. 13C NMR of 2-Bromo-1-[tert-butyl(dimethyl)silyloxy]-4,4-difluoro-3-phenylcyclopent-1-ene (6g).

13C NMR of 2-Bromo-1-[tert-butyl(dimethyl)silyloxy]-4,4-difluoro-3-phenylcyclopent-1-ene (6g)

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Figure S6. 19F NMR of 2-Bromo-1-[tert-butyl(dimethyl)silyloxy]-4,4-difluoro-3-phenylcyclopent-1-ene (6g).

19F NMR of 2-Bromo-1-[tert-butyl(dimethyl)silyloxy]-4,4-difluoro-3-phenylcyclopent-1-ene (6g)

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1H NMR of 1-[tert-Butyl(dimethyl)silyloxy]-5,5-difluoro-3-isopropyl-4-phenylcyclopent-1-ene (3i) and 3-[tert-Figure S7. 1H NMR of 1-[tert-Butyl(dimethyl)silyloxy]-5,5-difluoro-3-isopropyl-4-phenylcyclopent-1-ene (3i)and 3-[tert-Butyl(dimethyl)silyloxy]-4,4-difluoro-6-methyl-1-phenylhepta-2,5-diene (7i).

Butyl(dimethyl)silyloxy]-4,4-difluoro-6-methyl-1-phenylhepta-2,5-diene (7i)Page S8©

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13C NMR of 1-[tert-Butyl(dimethyl)silyloxy]-5,5-difluoro-3-isopropyl-4-phenylcyclopent-1-ene (3i) and 3-[tert-Figure S8. 13C NMR of 1-[tert-Butyl(dimethyl)silyloxy]-5,5-difluoro-3-isopropyl-4-phenylcyclopent-1-ene (3i)and 3-[tert-Butyl(dimethyl)silyloxy]-4,4-difluoro-6-methyl-1-phenylhepta-2,5-diene (7i).

Butyl(dimethyl)silyloxy]-4,4-difluoro-6-methyl-1-phenylhepta-2,5-diene (7i)Page S9©

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19F NMR of 1-[tert-Butyl(dimethyl)silyloxy]-5,5-difluoro-3-isopropyl-4-phenylcyclopent-1-ene (3i) and 3-[tert-Figure S9. 19F NMR of 1-[tert-Butyl(dimethyl)silyloxy]-5,5-difluoro-3-isopropyl-4-phenylcyclopent-1-ene (3i)and 3-[tert-Butyl(dimethyl)silyloxy]-4,4-difluoro-6-methyl-1-phenylhepta-2,5-diene (7i).

Butyl(dimethyl)silyloxy]-4,4-difluoro-6-methyl-1-phenylhepta-2,5-diene (7i)Page S10©

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Figure S10. NOE spectrum I of 5,5-difluorocyclopent-1-en-1-yl silyl ether 3i.

NOE spectrum I of 5,5-difluorocyclopent-1-en-1-yl silyl ether 3iPage S11©

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Figure S11. NOE spectrum II of 5,5-difluorocyclopent-1-en-1-yl silyl ether 3i.

NOE spectrum II of 5,5-difluorocyclopent-1-en-1-yl silyl ether 3iPage S12©

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1H NMR of 3,4-Dibutyl-1-[tert-butyl(dimethyl)silyloxy]-5,5-difluorocyclopent-1-ene (3j) and 7-[tert-Figure S12. 1H NMR of 3,4-Dibutyl-1-[tert-butyl(dimethyl)silyloxy]-5,5-difluorocyclopent-1-ene (3j) and 7[tert-Butyl(dimethyl)silyloxy]-6,6-difluorotrideca-4,7-diene (7j).

Butyl(dimethyl)silyloxy]-6,6-difluorotrideca-4,7-diene (7j)Page S13©

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13C NMR of 3,4-Dibutyl-1-[tert-butyl(dimethyl)silyloxy]-5,5-difluorocyclopent-1-ene (3j) and 7-[tert-Figure S13. 13C NMR of 3,4-Dibutyl-1-[tert-butyl(dimethyl)silyloxy]-5,5-difluorocyclopent-1-ene (3j) and 7[tert-Butyl(dimethyl)silyloxy]-6,6-difluorotrideca-4,7-diene (7j).

Butyl(dimethyl)silyloxy]-6,6-difluorotrideca-4,7-diene (7j)Page S14©

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19F NMR of 3,4-Dibutyl-1-[tert-butyl(dimethyl)silyloxy]-5,5-difluorocyclopent-1-ene (3j) and 7-[tert-Figure S14. 19F NMR of 3,4-Dibutyl-1-[tert-butyl(dimethyl)silyloxy]-5,5-difluorocyclopent-1-ene (3j) and 7[tert-Butyl(dimethyl)silyloxy]-6,6-difluorotrideca-4,7-diene (7j).

Butyl(dimethyl)silyloxy]-6,6-difluorotrideca-4,7-diene (7j)Page S15©

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