Syn th esis of 6H-Diben zo[b,d ]p yr a n -6-on es fr om Ar yl
3-Br om op r op en oa tes via a Sequ en tia l On e-P ot P r oced u r e Usin g
th e Son oga sh ir a Cou p lin g-Ben za n n u la tion Rea ction
Taishi Kawasaki and Yoshinori Yamamoto*
Department of Chemistry, Graduate School of Science, Tohoku University, Sendai, 980-8578, J apan
yoshi@yamamoto1.chem.tohoku.ac.jp
Received February 26, 2002
Various kinds of 6H-dibenzo[b,d]pyran-6-ones 4 were synthesized via a sequential one-pot procedure
using the Sonogashira coupling-benzannulation reaction of aryl 3-bromopropenoates 1, in which
the ortho-position of aryl group is substituted with enynes or iodine, with acetylenes 2 in the presence
of palladium and copper catalysts. The Sonogashira coupling between the aryl 3-bromopropenoates
1a and 1b, bearing enynes at the ortho-position of aryl group, and alkynes 2a -g gave the enyne
intermediates 3 in situ, which subsequently underwent the palladium-catalyzed benzannulation
reaction to afford the 6H-dibenzo[b,d]pyran-6-ones 5a -g and 6. The Sonogashira coupling between
the aryl 3-bromopropenoate 1c, bearing iodine at the ortho-position of aryl group, and diynes 2f
and 2h produced the diyne intermediates 13, which underwent the benzannulation reaction to
afford the 6H-dibenzo[b,d]pyran-6-ones 14f and 14h .
In tr od u ction
dibenzo[b,d]pyran-6-one skeletons accompanied by aro-
matization in a one-step procedure.4-9 For example,
cycloaddition-elimination sequences of coumarins4 or
3-nitrochromone,5 rearrangements of spiro compounds,6
biomimetic synthesis of alternariol derivatives,7 the
coupling reaction of an active quinone with phenols,8 and
cycloaromatization of endiynes9 are known. Recently, we
reported efficient methods for the construction of benzene
rings using palladium-catalyzed benzannulation reac-
tions, and we succeeded in synthesizing multifunction-
alized and polysubstituted benzenes.10 These methodolo-
6H-Dibenzo[b,d]pyran-6-ones are widespread in na-
ture1 and exhibit biological activities.2 They have also
been used as intermediates for the synthesis of more
complicated structural units and naturally occurring
substances.3 Although various methods have been re-
ported for the synthesis of 6H-dibenzo[b,d]pyran-6-ones,
few methods are known for the construction of 6H-
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10.1021/jo025659x CCC: $22.00 © 2002 American Chemical Society
Published on Web 06/01/2002
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J . Org. Chem. 2002, 67, 5138-5141