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Scheme
3 Formation of enantiomerically enriched cyclobutene
derivatives.
E : Z ratio of 93 : 7 but the absolute configuration of (E)-1a is
(S) whereas (Z)-1a has an (R) configuration, both formed with
an enantiomeric ratio 499 : 1. When transformed into the
corresponding cyclobutene 2a either with Pt(II) or Pd(II)
catalyst (condition described in Table 1, entries 1 and 7
respectively), a complete preservation of the stereochemical
information was also found as described in Scheme 3. As both
isomers (E)- and (Z)-1a were prepared with enantiomeric ratio
499 : 1, the 93 : 7 enantiomeric ratio of 2a corresponds to the
ratio of the two geometrical isomers.
8 K. Hiroi, H. Nakamura and T. Anzai, J. Am. Chem. Soc., 1987,
109, 1249.
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1; Methods of Organic Chemistry, Houben-Weyl, ed. A. de Meijere,
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10 Recent hydro- and carbometalation reactions of cyclopropenes:
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In conclusion, Pt(II)- and Pd(II)-catalyzed ring-expansion of
enantiomerically pure alkylidenecyclopropane derivatives
possessing a quaternary stereocenter proceeds smoothly and
leads to the corresponding cyclobutene species with complete
preservation of the stereochemical information.
This research was supported by the German-Israeli Project
Cooperation (DIP-F. 6.2) and by the Israel Science Foundation
administered by the Israel Academy of Sciences and
Humanities (grant No 459/04). The authors thank Dr C. Aıssa
¨
for preliminary studies. I.M. is holder of the Sir Michael and
Lady Sobell Academic Chair.
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18 Enantiomeric ratio couldn’t be determined on the cyclobutene 2f
by chiral HPLC. The absolute configuration was determined by
comparison with calculated CD (see ref. 17).
¨
19 The absolute configuration of the minor isomer wasn’t determined.
ꢀc
This journal is The Royal Society of Chemistry 2009
5762 | Chem. Commun., 2009, 5760–5762