ORGANIC
LETTERS
1999
Vol. 1, No. 3
435-437
Electrochemical Generation and
Reaction of o-Quinodimethanes from
{[[2-(2,2-Dibutyl-2-stannahexyl)phenyl]-
methyl]thio}benzenes
Madoka Jinno, Yoshikazu Kitano, Masahiro Tada, and Kazuhiro Chiba*
Laboratory of Bio-organic Chemistry, Tokyo UniVersity of Agriculture and Technology,
3-5-8 Saiwai-cho, Fuchu, Tokyo 183-8509, Japan
Received May 7, 1999
ABSTRACT
The anodic oxidation of {[[2-(2,2-dibutyl-2-stannahexyl)phenyl]methyl]thio}benzenes gave o-quinodimethanes which were trapped in situ by
dienophiles to give the corresponding cycloadducts in excellent yields. The electron transfer and succeeding 1,4-elimination reaction was
efficiently completed in a solution of lithium perchlorate/nitromethane in the presence of acetic acid. The reaction progress was quantitatively
controlled by the passage of charge. By using this new method, an aryltetralin lignan skeleton was also synthesized.
It has recently been demonstrated that electrochemical
oxidation provides a relatively efficient means of effecting
intermolecular carbon-carbon bond formation. The potential
of this electrochemical method is highlighted by the general
way in which electrochemistry can be used to generate
reactive intermediates to construct varied cycloadducts under
mild conditions. In this study, we aimed at accomplishing
the electrochemical generation and reaction of o-quino-
dimethanes, a goal which has been of great interest in the
synthesis of polycyclic compounds.1
the other hand, we anticipate that the electrochemical method
also has the potential to play an important role in the
generation of unstable o-quinodimethanes followed by their
cycloaddition with dienophiles. The method is further
expected to proceed under the quantitative control of the
chemical reaction by regulating the passed charge. Previ-
ously, a cathodic generation and Diels-Alder reaction of
o-quinodimethanes has been accomplished by using 1,2-bis-
(bromomethyl)benzene.6 Recently, we accomplished some
cycloaddition reactions by using an electrooxidative reaction
To date, various methods have been reported for the
generation of o-quinodimethane intermediates, including the
metal-,2 anion-,3 or acid-induced,4 thermal, or photochemical
elimination reaction5 of the corresponding precursors. On
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10.1021/ol990647s CCC: $18.00 © 1999 American Chemical Society
Published on Web 06/25/1999