G. C. Lloyd-Jones and A. Gordillo
1H NMR ([D6]DMSO, 500 MHz): d = 3.53 (dd, J=12.5, 2.9 Hz, 1H), 3.67
(dd, J=12.5, 2.5 Hz, 1H), 5.53–4.57 (m, 2H), 5.27 ppm (t, J=5.6 Hz, 2H,
OH).
Experimental Section
Kinetic studies (Figure 1 and Figure 2): GC conditions: HP-1 Agilent
Technologies column (30 m ꢂ 0.32 mm ID ꢂ 3.0 mm film thickness), injec-
tor: 2708C, oven: 3008C, 15 psi He (carrier gas). Analysis conditions:
758C, 5 min, 58Cminꢁ1 1808C, 5 min. Retention times: [allyl alcohol]:
1.9 min, [diallyl carbonate]: 12.9 min, [glycerol]: 15.5 min, [allyl glycerol]:
17.5 min, [glycerol carbonate]: 23.1 min, [allyl glycerol carbonate]:
25.6 min.
Reaction with meso-erythritol (1i): a mixture of diallyl carbonate (2,
0.22 mL, 1.50 mmol), meso-erythritol (1i, 123.3 mg, 1.0 mmol), triphenyl-
phosphine (20.98 mg, 80.0 mmol), [Pd2ACHTNUGTRENUNG(dba)3·dba] (23.00 mg, 20.0 mmol)
and degassed DMF (2 mL) was stirred at 258C for 24 h. The reaction
mixture was then analysed by 1H NMR spectroscopy (82% rac-4i, 5%
meso-4i). Purification by flash chromatography (dichloromethane/etha-
nol/triethylamine 100:2:2, Rf <0.1) on silica gel to give rac-4i as a color-
less oil. 1H NMR ([D6]DMSO, 500 MHz): d = 3.30–3.43 (m, 2H), 3.73–
3.78 (m, 1H), 4.43 (d, J=7.3 Hz, 2H), 4.77–4.85 (m, 2H), 5.44 ppm (d,
J=5.4 Hz, 1H); 13C{1H} NMR ([D6]DMSO, 125 MHz): d = 62.21, 65.22,
70.46, 77.49, 155.50. EI-MS (in THF): m/z (%): 148.03 (12) [M++H].
General procedure: In a 25 mL Schlenk tube, a mixture of diallyl carbon-
ate (2, 0.145 mL, 1.00 mmol), glycerol (1g, 92.1 mg, 1.0 mmol) and 5 mL
of degassed THF were stirred under atmosphere of N2(g) at room tem-
perature for 5 min. After addition of triphenylphosphine (10.49 mg,
40.0 mmol) and [Pd2ACHTUNGTRENNUNG(dba)3·dba] (11.50 mg, 10.0 mmol), the reaction mix-
ture was stirred at 258C. The reaction was sampled by withdrawing
0.1 mL aliquots and quenching into a GC vial containing 3.0 mg of 1,3-
bis(diphenylphosphino)propane (DPPP). Reaction conversion was moni-
tored by GC-FID (see Supporting Information for more detail); with
linear regression used to extract initial rates. Glycerol (1g) initial rate (3–
21 min): y=ꢁ4.71x + 185.61; R2 =0.9949; (ꢁ282.9 mmhꢁ1). Glycerol car-
bonate (4g) initial rate (0–28 min): y=3.23xꢁ0.89; R2 =0.9901;
(193.8 mmhꢁ1). For details of the kinetic simulations, please see Support-
ing Information.
Acknowledgements
A.G. thanks the Marie Curie Foundation for an IEF Fellowship. G.C.L.J.
is a Royal Society Wolfson Research Merit Award Holder.
24, 1793–1796; d) J. Tsuji, I. Shimizu, I. Minami, Y. Ohashi, T. Su-
General procedure for the reaction in presence of 13CO2
ACHTUNGTREN(NUNG Figure 3): In a
250 mL Schlenk tube, mixture of diallyl carbonate (2, 0.174 mL,
a
1.20 mmol), glycerol (1g, 92.1 mg, 1.0 mmol) and 5 mL of degassed THF
were stirred under an atmosphere of N2(g) at room temperature for
5 min. After the contents of the Schlenk tube had been frozen in N2(l)
and kept in vacuo for 5 s, 13CO2 was transferred directly from a glass
flask containing 250 mL (11.2 mmol) of gas at 1 bar of pressure. Then, tri-
8096; E. J. Stoner, M. J. Peterson, V. K. Grover, J. Org. Chem. 2003,
68, 8092–8096; f) E. J. Stoner, M. J. Peterson, M. S. Allen, J. A. De-
Mattei, A. R. Haight, M. R. Leanna, S. R. Patel, D. J. Plata, R. H.
21, 1176–1178; j) for reactions of phenols see: A.-A. G. Shaikh, S.
[6] L. Evans, N. Fey, J. N. Harvey, D. Hose, G. C. Lloyd-Jones, P.
Murray, A. G. Orpen, R. Osborn, G. J. J. Owen-Smith, M. Purdie, J.
[7] The rate enhancement does not arise from irreversible oxidative ad-
dition, see: a) C. Amatore, S. Gamez, A. Jutand, G. Meyer, M.
3376; b) S. Shekhar, B. Trantow, A. Leitner, J. F. Hartwig, J. Am.
phenylphosphine (10.49 mg, 40.0 mmol) and [Pd2ACTHNUTRGNEU(NG dba)3·dba] (11.50 mg,
10.0 mmol) were added and the reaction mixture warmed rapidly to 258C
and stirred magnetically. The reaction was sampled by withdrawing
0.1 mL aliquots, quenching these with 3.0 mg of 1,3-bis(diphenylphosphi-
no)propane (DPPP), and then removing the solvent in vacuo. The 13C in-
corporation in the products was calculated from the integration of the
13C{1H} NMR signals in the crude product and comparison with reference
spectra (see Supporting Information for full details).
General procedure for the synthesis of cyclic carbonates 4g, 4h and 4i:
In a 25 mL Schlenk tube, a mixture of diallyl carbonate (2) (0.14–
0.43 mL, 1.0–3.0 mmol), alcohol (1g–i, 1.00 mmol) and 2–5 mL of de-
gassed DMSO or DMF or THF were stirred under an atmosphere of
N2(g) at room temperature for 5 min. After addition of triphenylphos-
phine (40.0–160.0 mmol) and [Pd2ACHTNUTRGNENUG(dba)3·dba] (10.0–25.0 mmol), the
Schlenk tube was heated or cooled to the corresponding temperature for
3–24 h. The solvent was then removed in vacuo and the residue thus ob-
1
tained analysed by H NMR spectroscopy. Purification was performed by
flash column chromatography on silica gel.
Reaction with glycerol (1g): a mixture of diallyl carbonate (0.43 mL,
3.00 mmol), glycerol (1g) (92.1 mg, 1.0 mmol), triphenylphosphine
(26.22 mg, 100.0 mmol), [Pd2ACHTUNTRGNE(NUG dba)3·dba] (28.75 mg, 25.0 mmol) and 2 mL
of DMSO was stirred at 258C for 22 h. The reaction crude was then ana-
lyzed by 1H NMR spectroscopy (94% 4g, 6% 5g). Purification was per-
formed by flash column chromatography (hexane/ethyl acetate 1:1, Rf =
0.17) on silica gel to give 4g as a colorless oil. 1H NMR ([D6]DMSO,
500 MHz): d = 3.51 (ddd, J=12.6, 8.1, 3.4 Hz, 1H), 3.66 (ddd, J=12.6,
5.5, 2.8 Hz, 1H), 4.28 (dd, J=8.1, 5.9 Hz, 1H), 4.49 (t, J=8.1 Hz, 1H),
4.80 (m, 1H), 5.25 ppm (t, J=5.5 Hz, 1H, OH); 13C{1H} NMR
([D6]DMSO, 125 MHz): d = 61.02, 66.30, 77.45, 155.58 ppm; EI-MS (in
THF): m/z (%): 119 (27) [M++H].
[8] For a recent comprehensive review of decarboxylative allylation,
see: a) J. D. Weaver, A. Recio, A. J. Grenning, J. A. Tunge, Chem.
carboxylative processes, see: b) S.-L. You, L.-X. Dai, Angew. Chem.
[9] Approximately 10% transesterification of ethyl allyl carbonate to
diallyl carbonate was recently reported by Grenning and Tunge, in a
study of the deacylative allylation of ethyl cyanoactate derivatives;
Reaction with d,l-threitol (1h):
0.22 mL, 1.50 mmol), d,l-threitol (1h, 125.9 mg, 1.0 mmol), triphenyl-
phosphine (20.98 mg, 80.0 mmol), [Pd2A(dba)3·dba] (23.00 mg, 20.0 mmol)
A mixture of diallyl carbonate (2,
CTHUNGTRENNUNG
was stirred at 258C for 24 h. The reaction mixture was then analyzed by
1H NMR spectroscopy (53% rac-4h, 30% iso-4h). The final product was
purified by flash chromatography (dichloromethane/ethanol/triethyl-
amine 100:2:2, Rf <0.1) on silica gel to give iso-4h as a colorless oil.
[10] Yoshida and Ihara have developed intramolecular transesterification
routes for the synthesis of cyclic carbonates, employing propargylic
2664
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2012, 18, 2660 – 2665