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(R)-1-[(2,3-Dihydrobenzo[b][1,4]dioxin-6-yl)methyl]-3-(2-
methoxyphenyl)pyrrolidine (4)
Yield: 28.7 mg, 63%; ½a27 =À16.05 (c=1.19 in CHCl3); FTIR (KBr
D
~
neat): n=3029, 1590, 1507, 1461, 1432, 1289, 1241, 1068, 919, 887,
815, 754 cmÀ1 1H NMR (400 MHz, CDCl3): d=7.31 (dd, J=7.6,
;
1.6 Hz, 1H), 7.20–7.13 (m, 1H), 6.96–6.87 (m, 2H), 6.86–6.77 (m,
3H), 4.24 (s, 4H), 3.80 (s, 3H), 3.76–3.71 (m, 1H), 3.58 (s, 2H), 2.99
(t, J=8.8 Hz, 1H), 2.83–2.76 (m, 1H), 2.73–2.63 (m, 1H), 2.55–2.46
(m, 1H), 2.34–2.22 (m, 1H), 1.92–1.80 ppm (m, 1H); 13C NMR
(100 MHz, CDCl3): d=157.1, 143.2, 142.4, 133.5, 132.7, 127.4, 126.9,
121.8, 120.6, 117.6, 116.8, 110.4, 64.3, 60.5, 60.0, 55.3, 54.4, 36.4,
31.8 ppm; HRMS (FAB): m/z calcd for [C20H23NO3 +H]+ 326.1756;
found: 326.1757 [M+H]+.
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(R)-1-Benzyl-3-[2-(trifluoromethyl)phenyl]pyrrolidine (5)
Yield: 27.5 mg, 60%; ee was determined on a Daicel Chiralpak AD-
H
column eluting with hexane/isopropanol=99:1, flow=
0.1 mLminÀ1; retention times: 64.05 ((R)-enantiomer), 69.84 min
((S)-enantiomer); 96.5% ee; ½a23 = +18.79 (c=1.00 in CHCl3); FTIR
D
~
(KBr neat): n=2960, 2790, 1491, 1452, 1381, 1343, 1118, 1024, 756,
699 cmÀ1 1H NMR (400 MHz, CDCl3): d=7.66 (d, J=8.0 Hz, 1H),
;
7.53–7.39 (m, 2H), 7.32–7.21 (m, 4H), 7.20–7.12 (m, 2H), 3.73–3.65
(m, 1H), 3.64 (d, J=12.8 Hz, 1H), 3.56 (d, J=12.8 Hz, 1H), 2.87–2.75
(m, 2H), 2.64–2.49 (m, 2H), 2.36–2.24 (m, 1H), 1.82–1.78 ppm (m,
1H); 13C NMR (100 MHz, CDCl3): d=146.2, 139.3, 132.2, 128.75,
128.74, 128.3, 128.0 (q, J=29.0 Hz), 127.0, 125.7, 125.12 (q, J=
6.0 Hz), 124.6 (q, J=272.0 Hz), 62.9, 60.4, 54.9, 38.2, 35.0 ppm;
HRMS (FAB+): m/z: calcd for [C18H18F3N+Na]+ 328.1289; found:
328.1289 [M+Na]+.
Acknowledgements
Financial support from the Ministry of Science and Technology
of Republic of China (100-2113-003-009-MY2, 102-2113-003-
006-MY2) and the National Taiwan Normal University is
gratefully acknowledged.
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Keywords: chiral
enantioselectivity · pyrrolidine · rhodium
ligands
·
conjugate
addition
·
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Received: March 18, 2015
Published online on June 3, 2015
Chem. Eur. J. 2015, 21, 11050 – 11055
11055
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