PdCl2-Catalyzed Chlorocyclocarbonylation of Allenols
-catalyzed cyclization reactions of 2,3-allenoic acids/esters.6 In
addition, transition metal-catalyzed cyclocarbonylative cycliza-
tion reactions of (Z)-3-iodo-2-alkenols,7 2-bromoenals,8 (Z)-2-
iodoalkenyl aryl or alkyl ketones,9 terminal or internal propar-
gylic alcohols,10 3-aryl-2-alkynones,11 1,6-alkynals or hex-5-
ynoic acid pyridin-2-yl esters,12 terminal alkynes/H2O,13 and
4,6-di-tert-butylbenzofuran-2,3-dione/alkynes14 prove to be ef-
fective in constructing 2(5H)-furanones. However, reports
concerning the synthesis of 5,6-dihydropyran-2-ones through
metal-catalyzed cyclocarbonylation reactions are rare.15,16 In
2000, Takahashi et al.16 reported a successful cyclocarbonylation
of 2,3- or 3,4-allenols to form 2(5H)-furanones and 5,6-
dihydropyran-2-ones using a ruthenium catalyst. On the other
hand, we recently described a PdCl2-catalyzed chlorocyclocar-
bonylation of 2-alkynols for the efficient synthesis of (Z)-R-
chloroalkylidene-ꢀ-lactones.17 On the basis of these results, we
present here the regioselective chlorocyclocarbonylation of 2,3-
SCHEME 1
SCHEME 2
SCHEME 3
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or 3,4-allenols affording 3-chloromethyl-2(5H)-furanones and
3-chloromethyl-5,6-dihydropyran-2-ones, respectively.
Results and Discussion
Preparation of the Starting Materials. All of the terminal
2,3- or 3,4-allenols (1a-r or 2a-i) were synthesized by the
Crabbe´ homologation of the corresponding terminal alkynols,18
which were easily obtained via the Grignard reaction of ethynyl
magnesium bromide19 or allenyl magnesium bromide20 with
carbonyl compounds (Schemes 1 and 2). 2,3-Allenols 1s,t were
prepared from the reaction of the corresponding propargylic
bromides with aldehydes in the presence of NaI and SnCl2
(Scheme 3).21 2-Methyl-4-phenylbuta-2,3-dienol (1u) was pre-
pared by reduction of ethyl 2-methyl-4-phenyl-2,3-butadienoates
with DIBAL-H.22
Optically active (R)- or (S)-1a-d were also prepared via the
Crabbe´ reaction of the corresponding (R)- or (S)-propargylic
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J. Org. Chem. Vol. 73, No. 22, 2008 8961