Advanced Synthesis & Catalysis
10.1002/adsc.201701197
Financial support by the National Natural Science Foundation of
China (grant no 21572084, 21172098) and the Natural Science
Foundation Program of Gansu Province (1506RJZA224). We
thank Ms. Zheng min for her kind assistance and thank Mr. Paxtyn
benzofuran,bicyclo[4.2.0]octane]-7’-one based on 3-
diazochroman-4-one and alkene. The process involved
Rh (II)-catalyzed Wolff rearrangement/ [2+2]
cycloaddition reaction. Also, the 1,7-dioxa- M. Fisher for English writing revision.
spiro[4.4]nonan-2-one motif, a crucial intermediate in
the synthesis of the nature product, was procured
through the Baeyer-Villiger oxidation of the 6-oxa- References
spiro[3.4]octan-1-one. These two kinds of products
possess a special fused and spiro cyclic oxygen-
containing rigid skeleton structure are reported in this
article. A series of 3-diazochroman-4-one and alkene
were evaluated and corresponding products were
obtained in moderate to good yields. Considering its
broad substrate scope and good functional group
compatibility, this protocol may provide broad
applications in organic synthesis.
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Typical Procedure for the Preparation of 3
1
Under an argon atmosphere, 1 (1 mmol, 1.0 equiv) in 15ml
of CH Cl was added slowly to a solution with stirring, of 2
2 2
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(
2 4 2 2
5 mmol, 5.0 equiv) and Rh (Oct) (0.1 mol %) in CH Cl (5
ml) at 45 ℃ over 15 h by syringe pump. The reaction was
monitored by TLC. The reaction mixture was extracted three
times with EtOAc and water. The combined organic layer
was washed with saturated aqueous brine and dried over
4
MgSO . The filtrate was then filtered and concentrated in
vacuo. Further purification by a short silica gel column using
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To a 100 ml round-bottom bottle installed with an anhydrous
2 2
calcium chloride tube condenser, 10 ml CH Cl and 50% of
2 2
H O (2 ml, 20 mmol, 20.0 equiv ) was added. Then
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Cl
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was
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added to this mixture and refluxed for 1 hour. The reaction
was monitored by TLC. Then the reaction mixture was
2 2 3
extracted three times with CH Cl and NaHCO (10%), the
combined organic layer was washed with saturated aqueous
brine and dried over MgSO . The filtrate was then filtered
4
and concentrated in vacuo. Further purification by a short [6] a) H. J. Kabbe, A. Widdig, Angew. Chem. Int. Edit. 2010,
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needed to be separated by methylbenzene.
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Supporting Information
Detailed descriptions of experimental procedures and their
spectroscopic data, as well as the crystal structures, are
presented in the Supporting Information. CCDC-1571954
(
3aa), CCDC-1571955 (3ai), CCDC-1571956 (3ai’), [9] a) T. Sawada, M. Nakada, Adv. Synth. Catal. 2010, 347,
CCDC-1571957 (3af) and CCDC-1571958 (3ab) contain
the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The
1527-1532; b) H. M. L. Davies, L. M. Hodges, J. Org.
Chem. 2003, 34, 5683-5689; c) P. E. O'Bannon, W. P.
Dailey, J. Org. Chem. 1989, 54, 3101-3105.
Centre
via
Acknowledgements
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