Organic Letters
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substrates had little influence on the product selectivity. For
example, substrates bearing both para-substituted electron-
donating and -withdrawing substituents gave comparable
selectivity for the six-membered ring heterocycles (3a−c)
(entries 1−3). An allyl phenol bearing a sterically bulky p-tert-
butyl group (1d) gave the desired product (3d) in good
selectivity (entry 4), as did substrates with an α-naphthyl group
(entries 5 and 6).
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́ ́
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Good regioselectivity was also realized for meta-substituted
reactants forming six-membered ring dihydrocoumarins in
good yields (entry 7). The same selectivity occurred when the
reaction was carried out with o-methoxy and o-methyl groups
on the aromatic ring (entries 8 and 9). Substrates with two
different substituents (1j−k) also experienced cyclocarbonyla-
tion to form six-membered ring lactones in excellent
regioselectivity (entries 10 and 11). Clearly, these results
show that the cyclocarbonylation using the PdI2/L1 or L2
catalytic system is not sensitive to electronic or steric effects.
In conclusion, we have developed an efficient regioselective
cyclocarbonylation of 2-allyl phenols using a combination of
PdI2 as the metal catalyst source and 1,3,5,7-tetramethyl-6-
phenyl-2,4,8-trioxa-6-phosphaadamantane (L1) or 1,3,5,7-tetra-
methyl-6-tetradecyl-2,4,8-trioxa-6-phosphaadamantane (L2) as
a ligand. This method provides facile access to a variety of 3-
methyl-3,4-dihydrocoumarins in excellent regioselectivity and
good yields.
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ASSOCIATED CONTENT
■
S
* Supporting Information
Experimental procedures, characterization data, and NMR
spectra. This material is available free of charge via the Internet
AUTHOR INFORMATION
■
Corresponding Author
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful to Cytec Canada, Inc. and to the Natural
Sciences and Engineering Research Council (NSERC) for
support of this work. This paper is dedicated to the memory of
Prof. Dr. Armando Cabrera (1944−2014).
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