Synlett 2018; 29(04): 425-429
DOI: 10.1055/s-0036-1591720
cluster
© Georg Thieme Verlag Stuttgart · New York

Intramolecular Aminotrifluoromethanesulfinyloxylation of ω-Aminoalkenes by CF3SO2Na/Pd(OAc)2/PhI(OAc)2/ t BuOCl/PivOH System

Satoru Suzuki
a  Department of Life Science and Applied Chemistry, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan   Email: nozshiba@nitech.ac.jp
,
Tomohiro Kamo
a  Department of Life Science and Applied Chemistry, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan   Email: nozshiba@nitech.ac.jp
,
Kazunobu Fukushi
a  Department of Life Science and Applied Chemistry, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan   Email: nozshiba@nitech.ac.jp
,
b  Department of Nanopharmaceutical Sciences, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
,
a  Department of Life Science and Applied Chemistry, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan   Email: nozshiba@nitech.ac.jp
,
a  Department of Life Science and Applied Chemistry, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan   Email: nozshiba@nitech.ac.jp
b  Department of Nanopharmaceutical Sciences, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
› Author Affiliations
JSPS KAKENHI Grant Number JP 16H01142 in Middle Molecular Strategy.
Further Information

Publication History

Received: 15 September 2017

Accepted after revision: 16 October 2017

Publication Date:
13 November 2017 (online)

Published as part of the Cluster Alkene Halofunctionalization

Abstract

The first example of palladium-catalyzed intramolecular aminotrifluoromethanesulfinyloxylation of unactivated ω-aminoalkenes has been achieved. Reaction conditions are rather unique with a complex consisting of CF3SO2Na/Pd(OAc)2/PhI(OAc)2/ t BuOCl/PivOH to provide 6-endo-cyclized type products with a piperidine skeleton. Yields are moderate, and SO2 is not extruded. This method also provides the first synthesis of 3-trifluoromethanesulfinyloxy piperidine derivatives.

Supporting Information

 
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  • 18 General Procedure To a stirring mixture of ω-aminoalkenes 1 (0.1 mmol), PIDA (64.2 mg, 0.2 mmol, 2.0 equiv), Pd(OAc)2 (2.2 mg, 0.01 mmol, 10 mol%), CF3SO2Na (78.0 mg, 0.5 mmol, 5.0 equiv), and PivOH (51.0 mg, 0.5 mmol, 5.0 equiv) in MeCN (0.5 mL, 0.2 M) at 10 °C, t BuOCl (10.9 mg, 11 μL, 0.1 mmol, 1.0 equiv) was added under nitrogen atmosphere. The mixture was stirred at room temperature for 15 h. The resulting mixture was cooled to 0 °C, quenched with sat. NaHCO3 aqueous solution, and extracted with EtOAc three times. The combined organic layer was washed with brine, dried with Na2SO4, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (benzene/EtOAc = 98:2) to give product 3. 5,5-Dimethyl-1-tosylpiperidin-3-yl Trifluoromethanesulfinate (3a) 60% yield (dr = 54:46, mixture of diastereoisomer at sulfur atom); white solid.1H NMR (300 MHz, CDCl3): δ = 7.64 (q, J = 3.2 Hz, 2 H), 7.36–7.33 (m, 2 H), 4.82–4.68 (m, 1 H), 4.00 (q, J = 5.4 Hz, 0.5 H), 3.85 (q, J = 5.4 Hz, 0.5 H), 3.28 (d, J = 11.5 Hz, 0.5 H), 3.20 (d, J = 11.5 Hz, 0.5 H), 2.44 (s, 3 H), 2.37–2.30 (m, 1 H), 2.18 (d, J = 11.5 Hz, 0.5 H), 2.10 (d, J = 11.5 Hz, 0.5 H), 1.87 (td, J = 12.1, 4.6 Hz, 1 H), 1.43–1.26 (m, 1 H), 1.11 (s, 1.5 H), 1.10 (s, 1.5 H), 1.01 (s, 1.5 H), 0.99 (s, 1.5 H). 19F NMR (282 MHz, CDCl3): δ = –80.0 (major, s), –80.2 (minor, s). 13C NMR (176 MHz, CDCl3): δ = 143.9, 133.2, 129.8, 127.4, 127.3, 122.5 (q, J = 336.9 Hz), 122.4 (q, J = 336.0 Hz), 56.4, 56.3, 50.1, 50.0, 43.8, 43.5, 32.4, 32.3, 28.0, 27.9, 26.9, 24.9, 24.7, 21.4. IR (KBr) 2962, 2928, 1470, 1346, 1196, 1159, 1129, 950, 907, 857, 677 cm–1. ESI-MS: m/z = 422 [M + Na]+. ESI-HRMS: m/z calcd for C15H20NO4F3NaS2: 422.0684; found: 422.0679.
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  • 20 The 19F NMR (282 MHz) spectra of the mixture of CF3SO2Na (1.0 equiv), PivOH (1.0 equiv), and t BuOCl (1.0 equiv) in CD3CN indicated two singlet signals at δ = –74.01 ppm (CF3SO2Cl) and –77.14 ppm (7).
  • 21 The19F NMR (282 MHz) spectra of the mixture of 6 (1.0 equiv) and CF3SO2Na (1.0 equiv) in CD3CN indicated three singlet signals at δ = –73.98 ppm (CF3SO2Cl), –77.14 ppm (7), and –83.00 ppm (CF3SO2Na).