Synthesis and structure of a novel symmetrically substituted phosphatriptycene oxide

Full text of DOI:10.1080/10426500490429086

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Phosphorus, Sulfur, and Silicon and the Related
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SYNTHESIS AND STRUCTURE OF A NOVEL
SYMMETRICALLY SUBSTITUTED PHOSPHATRIPTYCENE
OXIDE
Junji Kobayashi a , Tomohiro Agou a & Takayuki Kawashima a
a University of Tokyo , Tokyo, Japan
Published online: 12 Aug 2010.
To cite this article: Junji Kobayashi , Tomohiro Agou & Takayuki Kawashima (2004) SYNTHESIS AND STRUCTURE OF A NOVEL
SYMMETRICALLY SUBSTITUTED PHOSPHATRIPTYCENE OXIDE, Phosphorus, Sulfur, and Silicon and the Related Elements, 179:4-5,
959-960, DOI: 10.1080/10426500490429086
To link to this article: http://dx.doi.org/10.1080/10426500490429086
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Phosphorus, Sulfur, and Silicon, 179:959–960, 2004
ꢀC
Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500490429086
SYNTHESIS AND STRUCTURE OF A NOVEL
SYMMETRICALLY SUBSTITUTED
PHOSPHATRIPTYCENE OXIDE
Junji Kobayashi, Tomohiro Agou, and Takayuki Kawashima
University of Tokyo, Tokyo, Japan
(Received August 17, 2003; accepted October 3, 2003)
Keywords: Derivatives; phosphatriptycene oxide
Heterotriptycenes bearing one or two heteroatoms at bridgehead posi-
tions have been widely investigated, and phosphatriptycenes are one
of attractive targets because electronic and structural properties of
the bridgehead can be studied by 31P NMR. Since the first synthe-
sis of a phosphatriptycene in 1974,1 there have been two other ex-
amples reported.2 However, their synthetic routes were complicated
and not suitable in the case of multifunctionalized substrates. Here
we report the synthesis of phosphatriptycene oxide 1 from tris(3-
methoxyphenyl)phosphine oxide 2 in moderate yield by two steps.
Direct lithiation of 2 with t-BuLi, followed by the reaction with
diphenyl carbonate gave the corresponding phenoxycarbonyl derivative
3 in 29% yield. Phosphatriptycene oxide 1 was synthesized in 52% yield
via intramolecular cyclization by treatment of 3 with 2 equivalents of
lithium diisopropylamide.
SCHEME 1
The study was partially supported by the Grant in Aid for the 21st Century COE
Program for Frontiers in Fundamental Chemistry.
Address correspondence to Junji Kobayashi, Department of Chemistry, Graduate
School of Science, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
E-mail: jkoba@chem.s.u-tokyo.ac.jp
959

960
J. Kobayashi et al.
31P NMR signal of 1 was observed at δP 2.0, which is 28 ppm upfield
shifted compared to that of 2 (δP 30.3). Such an upfield shift attributable
to the distortion around the phosphorus atom was also observed in the
reported phosphatriptycenes. Its crystal structure was determined by
x-ray crystallographic analysis.
Phosphatriptycene oxide 1 easily was converted to the corresponding
phosphatripticene and other chalcogenides in good yields.
REFERENCES
[1] C. Jongsma, J. P. de Kleijn, and F. Bickelhaupt, Tetrahedron, 30, 3465 (1974).
[2] a) D. Hellwinkel, W. Schenk, and W. Blaicher, Chem. Ber., 111, 1798 (1978); b) K. G.
Weinberg and E. B. Whipple, J. Am. Chem. Soc., 93, 1801 (1971).