FULL PAPERS
Gold(I)-Catalyzed Synthesis of Unsymmetrical Ethers
Preparation of 18O-Labelled Benzyl Alcohol
J=7.7 Hz, 6H), 7.25 (t, J=7.2 Hz, 3H), 4.04 (s, 1H), 3.26
(dd, J=8.9, 4.1 Hz, 1H), 2.74 (t, J=8.5 Hz, 1H), 1.82–1.61
(m, 1H), 0.96 (s, 3H), 0.95 (s, 3H), 0.87 (s, 3H); 13C NMR
(150 MHz, DMSO-d6): d=144.12, 128.21, 127.77, 126.84,
85.90, 70.14, 65.02, 44.04, 27.64, 26.74, 13.25; IR (thin film):
n=3458, 3086, 3058, 3032, 2970, 2927, 2882, 1958, 1727,
1631, 1597, 1490, 1449, 1384, 1176, 1154, 1060, 776, 766, 705,
648, 633, 510 cmÀ1; HR-MS (ESI): m/z=383.1978, calcd. for
C25H28O2Na: 383.2019.
Sodium (0.05 g) was added to 18O-labelled water (0.75 mL,
98% 18OH2) in a flask, and then 1-chloromethylbenzene
(0.5 mL) was added into the flask. The mixture was heated
to 958C and refluxed for 48 h with continuous stirring. The
product was purified by flash column chromatography and
C6H5CH218OH (0.25 g) was obtained. The 18O enriched
benzyl alcohol was examined by GC-MS, and the abundance
of C6H5CH218OH was determined to be 98%.
(1R,3aR,4S,7aR)-7a-Methyl-1-[(S)-1-(trityloxy)propan-2-
yl]octahydro-1H-inden-4-yl benzoate (5p): white solid;
yield: 95% yield (EtOAc/petroleum ether=1:50); mp 89.5–
90.98C; 1H NMR (600 MHz, DMSO-d6): d=7.95 (d, J=
7.9 Hz, 2H), 7.64 (t, J=7.3 Hz, 1H), 7.52 (t, J=7.6 Hz, 2H),
7.37 (d, J=8.0 Hz, 6H), 7.33 (t, J=7.6 Hz, 6H), 7.24 (t, J=
7.1 Hz, 3H), 5.26 (d, J=1.9 Hz, 1H), 3.06 (dd, J=8.8,
2.9 Hz, 1H), 2.70–2.65 (m, 1H), 1.98 (d, J=12.6 Hz, 1H),
1.84 (d, J=14.0 Hz, 1H), 1.71 (dt, J=13.7, 8.5 Hz, 1H),
1.60–1.45 (m, 4H), 1.39–1.31 (m, 2H), 1.26–1.16 (m, 4H),
1.10 (d, J=6.5 Hz, 3H), 0.94 (s, 3H); 13C NMR (150 MHz,
DMSO-d6): d=165.45, 144.06, 133.11, 130.13, 128.95, 128.73,
128.18, 127.75, 126.84, 85.56, 71.51, 67.28, 52.59, 50.38, 41.33,
36.39, 29.82, 25.90, 22.13, 17.50, 13.14; IR (thin film): n=
3450, 3059, 3021, 2920, 2851, 1958, 1640, 1596, 1493, 1447,
1384, 1133, 1078, 1031, 759, 735, 700, 619, 606, 494,
Acknowledgements
We thank the following for financial support: the National
Natural Science Foundation of China (Grants 21202103), the
Natural Science Foundation of Liaoning Province of China
(Grants 2014020080). We acknowledge the program for inno-
vative research team of the Ministry of Education and pro-
gram for Liaoning innovative research team in university. We
thank Prof. Ping Gong (Shenyang Pharmaceutical Universi-
ty) for facilities support and Mr. Patrick Michael Barbour
(University of Colorado at Boulder) for the assistance in
manuscript preparation.
468 cmÀ1
;
HR-MS (ESI): m/z=581.3023, calcd. for
References
C38H52O2SiNa: 581.3026.
tert-Butyldimethyl{[(1R,3aR,4S,7aR)-7a-methyl-1-[(S)-1-
(trityloxy)propan-2-yl]octahydro-1H-inden-4-yl]oxy}silane
(5q): Colorless oil; yield: 92% (EtOAc/petroleum ether=
1:50); 1H NMR (600 MHz, CDCl3): d=7.45 (d, J=7.6 Hz,
6H), 7.29 (t, J=7.7 Hz, 6H), 7.22 (t, J=7.3 Hz, 3H), 3.97
(d, J=1.9 Hz, 1H), 3.12 (dd, J=8.7, 3.2 Hz, 1H), 2.74–2.69
(m, 1H), 1.97 (d, J=12.4 Hz, 1H), 1.80 (dt, J=13.8, 3.7 Hz,
1H), 1.69–1.59 (m, 2H), 1.51–1.40 (m, 2H), 1.40–1.33 (m,
2H), 1.25–1.15 (m, 2H), 1.15–1.05 (m, 5H), 1.04–0.95 (m,
1H), 0.95–0.85 (m, 12H), 0.00 (s, 3H), À0.02 (s, 3H);
13C NMR (150 MHz, CDCl3): d=144.86, 129.04, 127.82,
126.94, 86.25, 69.62, 68.22, 53.91, 53.06, 42.39, 40.86, 37.16,
34.68, 26.86, 26.04, 23.32, 18.25, 17.99, 17.88, 13.92, À4.58,
À4.94; IR (thin film): n=3449, 3059, 3023, 2927, 2853, 1643,
1490, 1471, 1449, 1385, 1165, 1129, 1093, 1070, 1024, 775,
704, 619 cmÀ1; HR-MS (ESI): m/z=591.3624, calcd. for
C38H52O2SiNa: 591.3629.
(2S,3R,4R,5S,6R)-3-{[(2,2,2-Trichloroethoxy)carbonyl]-
amino}-6-[(trityloxy)methyl]tetrahydro-2H-pyran-2,4,5-triyl
triacetate (5r): White solid; yield: 73% (EtOAc/petroleum
ether=1:6); mp 107.9–109.28C; 1H NMR (600 MHz,
DMSO-d6): d=8.21 (d, J=9.1 Hz, 1H), 7.40–7.30 (m, 12H),
7.26 (t, J=6.5 Hz, 3H), 6.13 (d, J=3.4 Hz, 1H), 5.25 (t, J=
9.9 Hz, 1H), 5.16 (t, J=10.2 Hz, 1H), 4.97 (d, J=12.5 Hz,
1H), 4.75 (d, J=12.5 Hz, 1H), 4.17–4.07 (m, 1H), 3.99 (d,
J=10.1 Hz, 1H), 3.19 (d, J=9.9 Hz, 1H), 2.88 (dd, J=10.8,
3.2 Hz, 1H), 2.13 (s, 3H), 1.90 (s, 3H), 1.71 (s, 3H);
13C NMR (150 MHz, CDCl3): d=171.65, 168.85, 154.29,
145.47, 143.68, 129.89, 128.92, 128.13, 128.02, 127.97, 127.92,
127.23, 95.50, 90.89, 86.79, 74.88, 71.41, 71.18, 68.18, 61.61,
53.62, 21.16, 20.92, 20.83, 20.62; IR (thin film): n=3437,
3060, 2921, 2851, 1756, 1643, 1450, 1384, 1218, 1129, 1034,
821, 746, 705, 633, 619, 477 cmÀ1; HR-MS (ESI): m/z=
744.1181, calcd. for C34H34ClNO10Na: 744.1210.
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