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Synthesis 2008(23): 3805-3809  
DOI: 10.1055/s-0028-1083220
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

A Convenient Route to Synthesize N-Protected α,α-Difluorohomoallylic Amines by gem-Difluoroallylation of α-Amido Sulfones

Zheng-Feng Xiea, Zhuo Chaib, Gang Zhao*b, Ji-De Wang*a
a Education Ministry Key Laboratory of Oil & Gas Fine Chemicals, Xinjiang University, Urumqi 830046, P. R. of China
e-Mail: awangjdl@xju.edu.cn;
b Key Laboratory of Organofluorine Chemistry and Laboratory of Modern Synthetic Organic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, P. R. of China
Fax: +86(21)64166128; e-Mail: zhaog@mail.sioc.ac.cn;
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Publication History

Received 10 June 2008
Publication Date:
14 November 2008 (online)

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Abstract

A simple, mild, and efficient synthesis of α,α-difluorohomoallylic amines was achieved by the gem-difluoroallylation of α-amido sulfones with zinc powder.

Key words

fluorine compounds - allylations - amines - amido sulfones - zinc - ring-closing metathesis

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8

Characterization data for 5: colorless crystals; mp 96-97 ˚C. IR (film): 2925, 2855, 1707, 1456, 1408, 1393, 1168, 1092, 698 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 7.32 (m, 5 H), 6.26 (m, 1 H), 6.09 (m, 1 H), 5.74 (m, 1 H), 4.48-4.38 (m, 1 H), 3.56-3.47 (m, 13 H), 1.49 (s, 9 H). ¹³C NMR (75 MHz, CDCl3): δ = 154.1, 134.9, 133.6, 128.4, 128.2, 128.0, 122.1 (dd, J = 17.3, 25.1 Hz), 115.9 (t, J = 9 Hz), 120.6 (t, J = 177.5 Hz), 81.2, 59.1, 40.6, 27.2 (3 C). ¹9F NMR (282 MHz, CDCl3): δ = -79.56 (d, J F,F = 279.2 Hz), -103.24 (d, J F,F = 297.2 Hz). MS (ESI): m/z = 318 [M + Na]+. HRMS (EI): m/z calcd for C11H10NF2 [M+-Boc]: 194.0781; found: 194.0777.