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Synlett 2012(3): 473-477  
DOI: 10.1055/s-0031-1290314
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Platinum-Catalyzed Transformation of Alkyne Allyl Alcohols and Sulfonamides into Heterotricyclo[3.3.1.02,8]nonanes

So Hee Sim, Youjung Park, Young Keun Chung*
Intelligent Textile System Research Center and Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul 151-474, Korea
Fax: +82(2)8890310; e-Mail: ykchung@snu.ac.kr;
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Publication History

Received 14 November 2011
Publication Date:
19 January 2012 (online)

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Abstract

Platinum chloride catalyzed cycloisomerization of alkyne allyl alcohols and alkyne allyl sulfonamides gave new cycloisomerization products, diaza-, azaoxa-, and dioxatricyclo-[3.3.1.0²,8]nonanes, in reasonable to high yields.

Key words

alkyne allyl alcohols - alkyne allyl sulfonamides - platinum chloride - cycloisomerization - nucleophilic attack

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11

The synthetic procedures and spectroscopic data of the new compounds are summarized in the Supporting Information. CCDC-813816 (8B) contains the supplementary crystallo-graphic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

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General Procedure: To a flame-dried 10-mL Schlenk flask capped with a rubber septum, dioxane (2 mL) and PtCl4 (5 mg, 10 mol%) were added under N2 flow. To the flask, 1 (44 mg, 0.15 mmol) was added under N2. The reaction mixture was stirred at 90 ˚C and was monitored by TLC. After the reaction mixture was cooled to r.t., the reaction mixture was filtered and all the solvent was evaporated under reduced pressure. A flash column chromatography on a silica gel eluting with n-hexane and Et2O (8:2) gave 1B in 80% yield.

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1B: ¹H NMR (300 MHz, CDCl3): δ = 7.78 (d, J = 8.2 Hz, 2 H), 7.29 (d, J = 8.3 Hz, 2 H), 5.62 (s, 1 H), 4.00 (dd, J = 11.5, 5.5 Hz, 1 H), 3.83 (dd, J = 11.5, 3.5 Hz, 1 H), 3.41 (d, J = 11.4 Hz, 1 H), 3.12 (d, J = 11.5 Hz, 1 H), 2.43 (s, 3 H), 2.03 (dd, J = 12.7, 3.8 Hz, 1 H), 1.87 (d, J = 12.5 Hz, 1 H), 1.13 (s, 3 H), 0.96 (d, J = 6.1 Hz, 1 H), 0.83 (dd, J = 8.3, 5.8 Hz, 1 H). ¹³C NMR (75 MHz, CDCl3): δ = 143.5, 135.3, 129.5, 128.2, 78.7, 58.2, 39.7, 32.1, 24.0, 21.8, 20.1, 18.9, 12.0. HRMS (EI): m/z calcd for C15H19O3NS: 293.1086; found: 293.1087.

14

14B:¹H NMR (300 MHz, CDCl3): δ = 7.76 (d, J = 8.2 Hz, 4 H), 7.30 (d, J = 8.1 Hz, 4 H), 6.10 (t, J = 3.2 Hz, 1 H), 3.79 (m, 2 H), 3.13 (d, J = 12.2 Hz, 2 H), 2.43 (s, 6 H), 1.74 (d, J = 3.2 Hz, 2 H), 0.96 (s, 3 H), 0.92 (s, 2 H). ¹³C NMR (75 MHz, CDCl3): δ = 143.8, 135.7, 129.8, 127.9, 63.8, 38.5, 33.0, 23.9, 21.8, 18.4, 12.9. HRMS (EI): m/z calcd for C22H26O4N2S2: 446.1334; found: 446.1332.