pargyl alcohols (1) and CO2 in the presence of transition metal
compounds8-10 or tertiary phosphines11 as shown in eq 1.
Although such cyclic carbonate products are versatile intermedi-
ates or precursors in organic synthesis12 and polymer chemis-
try,13 the reaction scopes remain unclear especially for the
internal propargylic alcohols leading to R-alkylidene carbonates.
Inoue et al. reported a facile reaction of 4-hydroxy-4-methyl-
1-phenyl-2-pentyn-1-one (R1 ) C6H5C(dO) in eq 1) with CO2
in triethylamine without catalysts giving (E)-4-benzoylmethyl-
ene-5,5-dimethyl-1,3-dioxolan-2-one,14 while the Z-carbonate
products are obtainable in a range of 15-35% yield from
conjugated alkynol having a phenyl or allenyl group under basic
conditions.7c In addition, Dixneuf et al. reported the reaction of
conjugated propargyl alcohols with CO2 catalyzed by tri-n-
butylphosphine, P(n-C4H9)3, leading to cyclic carbonates without
stereochemical information.11b
Stereoselective Formation of r-Alkylidene Cyclic
Carbonates via Carboxylative Cyclization of
Propargyl Alcohols in Supercritical
Carbon Dioxide
Yoshihito Kayaki, Masafumi Yamamoto, and Takao Ikariya*
Graduate School of Science and Engineering, Tokyo Institute of
Technology, O-okayama, Meguro-ku, Tokyo 152-8552, Japan
ReceiVed October 9, 2006
Carboxylative cyclization of propargyl alcohols in super-
critical carbon dioxide (scCO2) containing P(n-C4H9)3 as a
catalyst proceeded smoothly to give R-alkylidene-1,3-diox-
olan-2-ones. Internal propargyl alcohols afforded Z-alkyl-
idene cyclic carbonates exclusively. CO2 incorporation was
markedly promoted under supercritical conditions, possibly
due to the facile formation of a putative P(n-C4H9)3-CO2
adduct as a key intermediate.
Recently, we have found that supercritical CO2 (scCO2)
effectively promotes the direct formation of cyclic urethanes
(4) Pd-catalyzed reaction of vinyl epoxides and CO2: (a) Fujinami, T.;
Suzuki, T.; Kamiya, M.; Fukuzawa, S.; Sakai, S. Chem. Lett. 1985, 14,
199-200. (b) Trost, B. M.; Angle, S. R. J. Am. Chem. Soc. 1985, 107,
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W.; Riley, D. J. J. Org. Chem. 1995, 60, 6205-6207. (b) Sakakura, T.;
Saito, T.; Okano, M.; Choi, J.-C.; Sako, T. J. Org. Chem. 1998, 63, 7095-
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T. J. Org. Chem. 1999, 64, 4506-4508. (d) Isaacs, N. S.; O’Sullivan, B.;
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Ikeda, Y.; Sakaihoti, T.; Fujimoto, K. J. Catal. 2000, 192, 355-362. (f)
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A large body of work has been devoted over the past decades
to the use of CO2 as an environmentally benign C1 feedstock
for the production of useful chemical commodities.1 For
example, the direct synthesis of carbonates2 from the reaction
of CO2 and epoxides3,4 or alcohols5-7 has been widely exploited
as an alternative to phosgene processes. Five-membered cyclic
carbonates, 1,3-dioxolan-2-ones, are also accessible from pro-
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J. Org. Chem. 1986, 51, 5499-5501. (b) Inoue, Y.; Itoh, Y.; Yen, I.-F.;
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Bull. Chem. Soc. Jpn. 1987, 60, 1204-1206.
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* Corresponding author. Phone: +81 3 5734 2636. Fax: +81 3 5734 2637.
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10.1021/jo062094m CCC: $37.00 © 2007 American Chemical Society
Published on Web 12/22/2006
J. Org. Chem. 2007, 72, 647-649
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