LETTER
Electrophilic Routes to Tertiary Adamantyl and Diamantyl Phosphonium Salts
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Figure 2 Three X-ray structures of phosphodiamantanes; A: 12; B:
13; C: 14; crystallographic numbering. ORTEP-3 diagrams are shown
with ellipsoids at 40% probability. Key data: 12: R = 0.0353, wR =
0.0408; 13: R = 0.0410, wR = 0.0479; 14: R = 0.0517, wR = 0.0622.
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Supporting Information for this article is available online at
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Acknowledgment
We thank the University of Jaffna for granting leave to J.P., and the
Clarendon Fund (Oxford) for an award.
(23) Olah, G. A.; Prakash, G. K. S.; Shih, J. G.; Krishnamurthy,
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(24) CCDC files 824773-824775 contain the supplementary
crystallographic data. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre
(25) The related t-Bu3PH cation appears frequently in the CCDC
crystallographic database. The average C–P bond length (13
structures) is 1.863 Å; c.f. 1.883 Å in 14.
(26) Fletcher, D. A.; McMeeking, R. F.; Parkin, D. J. Chem. Inf.
Comp. Sci. 1996, 36, 746.
References and Notes
(1) Present address: Dept. of Chemistry, University of Jaffna,
Jaffna, Sri Lanka.
(2) Littke, A. F.; Fu, G. C. J. Org. Chem. 1999, 64, 10; ref. 10
therein summarises earlier work..
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2002, 41, 1760. (c) Barrios-Landeros, F.; Carrow, B. P.;
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Science 2009, 325, 1661.
(5) Stambuli, J. P.; Buehl, M.; Hartwig, J. F. J. Am. Chem. Soc.
2002, 124, 9346.
(6) Despite the presumed non-existence of authentic (1-Ad)3P, it
is cited in Chemical Abstracts in four distinct patents.
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Schmutzler, R.; Rankin, D. W. H. Struct. Chem. 2011, 22,
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Okamoto, K. Tetrahedron 1987, 43, 701.
(28) Experimental data:
Caution: The tertiary triflates 2 and 10 are powerful
electrophiles and should be treated with care; avoid contact.
Sample Preparation 11 and 12 via 10: Anhydrous AgOTf
(105 mg, 0.4 mmol) was added to a solution of 1-
bromodiamantane (100 mg, 0.37 mmol) in anhyd 2,2-
dimethylbutane (10 mL) at 0 °C and stirred with exclusion of
light for 1.5 h. The solution was filtered under argon by
cannula and the solvent was removed under vacuum at 0 °C
to afford 1-diamantyl triflate(10) as colourless crystals. 1H
NMR (500 MHz, CDCl3, 25 °C): d = 1.54–2.40 (m). 13
C
(10) Lavrova, E. A.; Koidan, G. N.; Marchenko, A. P.; Pinchuk,
NMR (125 MHz, CDCl3, 25 °C): d = 118.7 (q, JCF = 316.7
Hz, CF3), 109.9 (C1), 43.6 (C10), 42.9 (C2), 42.4 (C7), 37.9
(C5), 36.8 (C8), 36.4 (C6), 32.8 (C3), 32.1 (C9), 24.8 (C4).
After repeating on a 1.2-millimolar scale and cannula
filtration HPPh2 (210 mg, 196 mL, 1.12 mmol)was added and
the solution was warmed to r.t. After 2 h stirring at r.t., a
white solid precipitated. Solvent was removed and the solid
A. M. J. Gen. Chem. USSR. 1995, 64, 1393.
(11) (a) Tewari, A.; Hein, M.; Zapf, A.; Beller, M. Synthesis
2004, 935. (b) Zapf, A.; Jackstell, R.; Rataboul, F.;
Riermeier, T.; Monsees, A.; Fuhrmann, C.; Shaikh, N.;
Dingerdissen, U.; Beller, M. Chem. Commun. 2004, 38.
(c) Neumann, H.; Brennfuehrer, A.; Gross, P.; Riermeier, T.;
Synlett 2011, No. 16, 2351–2354 © Thieme Stuttgart · New York