LETTER
Platinum-Catalyzed Synthesis of Heterotricyclo[3.3.1.02,8]nonanes
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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
(12) 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.
(13) 1B: 1H NMR (300 MHz, CDCl3): d = 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): d = 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): d = 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): d = 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.
(15) For an activation of a double bond by platinum catalyst, see:
Bell, F.; Holland, J.; Green, J. C.; Gagné, M. R.
Organometallics 2009, 28, 2038.
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© Thieme Stuttgart · New York
Synlett 2012, 23, 473–477