40.67 (OCH3), 29.13 (CHCH2CH2), 28.43 (CHCH2CH2), 17.41
(CH2CH2CH2), 14.98 (CHCH3 High Resolution Mass Spectrum
[FAB(+)]: m/z calcd for C9H15N2O2 [M + H]+ 183.1134, found
183.1149.
1.18-1.05 (m, 1H, CHCHHCH2), 1.00 (d, J 6.0, 3H, CHCH3).
=
dC (100 Hz, CDCl3) 155.10 (NCO2), 117.60 (CHC N), 53.31
=
(CH2CHC N(N)), 44.30 (CH2CH2N), 41.43 (OCH3), 36.16
(CHCH2CH), 32.89 (CHCH2CH2), 27.10 (CH2CHCH2(CH3)),
21.31 (CHCH3). High Resolution Mass Spectrum [FAB(+)]: m/z
calcd for C9H15N2O2 [M + H]+ 183.1134, found 183.1151.
cis-1-tert-Butoxycarbonyl-2-cyano-6-ethylpiperidine (2h). For
preparation see general procedure for electrochemical cyanation
(undivided cell).
cis-4-Acetoxy-2-cyano-1-methoxycarbonylpiperidine (2m). For
preparation see general procedure for electrochemical cyanation
(undivided cell).
n
max/cm-1 (neat): 2969, 2940, 1693, 1458, 1393, 1366, 1337, 1171.
=
dH (400 MHz, CDCl3) 5.17 (br s, 1H, CH2CHC N(N)), 4.11 (br s,
1H, CH2CHCH2(N)), 2.05-1.46 (m, 8H, CHCH2CH2CH2CH and
CHCH2CH3), 1.49 (s, 9H, C(CH3)3), 0.94 (t, J 7.3, 3H, CH2CH3).
n
max/cm-1 (neat): 2961, 2936, 2239, 1743, 1705, 1449. dH
=
(500 MHz, CDCl3) 5.39-5.27 (m, 1H, CH2CHC N(N)), 5.14 (t,
J 3.5, 1H, CH2CH(CH2)OAc), 4.20-3.95 (m, 1H, CH2CHHN),
3.78 (s, 3H, OCH3), 3.49-3.30 (m, 1H, CH2CHHN), 2.31
(d, J 15.5, 1H, CHCHHCH), 2.16 (s, 3H, OCH3), 1.96-1.88
(m, 2H, CH2CHHCH and CHCHHCH), 1.78-1.70 (m, 1H,
CH2CHHCH). dC (100 Hz, CDCl3) 169.90 (NCO2), 116.57
(CHC N), 67.51 (O2CCH3), 53.61 (CH2CHC N(N)), 43.44
(CH2CH(CH2)OAc), 39.80 (CH2CH2N), 33.15 (OCH3), 30.33
(OCH3 and CHCH2CH), 21.03 (CH2CH2CH). High Resolution
Mass Spectrum [EI(+)]: m/z calcd for C10H14N2O4 [M]+ 226.0953,
found 226.0927.
=
dC (100 Hz, CDCl3) 154.98 (NCO2), 119.88 (CHC N), 81.14
=
(CH2CHC N(N)), 52.54 (CH2CHCH2(N)), 40.37 (OC(CH3)3),
28.42 (CHCH2CH2), 28.18 (CHCH2CH2), 26.62 (CHCH2CH3),
24.30 (C(CH3)3), 15.33 (CH2CH2CH2), 11.34 (CH2CH3). High
Resolution Mass Spectrum [EI(+)]: m/z calcd for C13H22N2O2
[M]+ 238.1682, found 238.1667.
=
=
cis-5-Cyano-1-tritylproline methyl ester (2i). For preparation
see general procedure for electrochemical cyanation (undivided
cell).
Anal. Calc. for C26H24N2O2: C, 78.76; H, 6.10; N, 7.07. Found:
C, 78.58; H, 6.00; N, 6.95. nmax/cm-1 (neat): 3020, 2926, 2237,
1751, 1597, 1489, 1448. dH (500 MHz, CDCl3) 7.60 (d, J 7, 6H,
3 ¥ o-ArH2), 7.31 (t, J 8, 6H, 3 ¥ m-ArH2), 7.22 (t, J 8, 3H, 3 ¥
trans-2m. dH (500 MHz, CDCl3) 5.50-5.28 (m, 1H,
=
CH2CHC N(N)), 5.12-5.04 (m, 1H, CH2CH(CH2)OAc), 4.31-
4.10 (m, 1H, CH2CHHN), 3.77 (s, 3H, OCH3), 3.25-3.10 (m, 1H,
CH2CHHN), 2.29 (dt, J 13.0, 2.5, 1H, CHCHHCH), 2.18-2.11
(m, 1H, CHCHHCH), 2.06 (s, 3H, OCH3), 1.78 (td, J 13.5, 5.5,
1H, CHCHHCH2), 1.55-1.45 (m, 1H, CHCHHCH2).
=
p-ArH), 4.19 (dd, J 5.5, 3.5, 1H, CH2CHC N(N)), 4.03 (dd, J
5.0, 4.0, 1H, CH2CHCO2(N), 3.82 (s, 3H, OCH3), 1.80-1.72 (m,
2H, CHCH2CH2), 1.24-1.20 (m, 1H, CHCHHCH2), 0.86-0.83
(m, 1H, CHCHHCH2). dC (100 Hz, CDCl3) 175.21 (CHCO2),
143.35 (3 ¥ ArC), 128.97(3 ¥ o-ArC2), 128.27 (3 ¥ m-ArC2),
cis-2-Cyano-1-methoxycarbonyl-4-methoxypiperidine (2n). For
preparation see general procedure for electrochemical cyanation
(undivided cell).
=
127.00 (3 ¥ p-ArC), 121.60 (CHC N), 78.87 (NC(ArC)3), 64.17
=
(CH2CHC N(N)), 53.35 (CH2CHCO2), 52.13 (OCH3), 30.97
n
max/cm-1 (neat): 2961, 2936, 2239, 1717, 1705, 1449. dH
(CHCH2CH2), 30.18 (CHCH2CH2).
=
(300 MHz, CDCl3) 5.35-5.08 (m, 1H, CH2CHC N(N)), 4.05-
3.82 (m, 1H, CH2CHHN), 3.76 (s, 3H, OCH3), 3.66 (t, J
3.0, 1H, CH2CHHN), 3.42 (s, 3H, OCH3), 3.48-3.31 (m, 1H,
CH2CH(CH)OCH3), 2.41-2.25 (m, 1H, CHCHHCH), 2.08-
1.92 (m, 1H, CHCHHCH), 1.85-1.52 (m, 2H, CHCH2CH2).
5-Cyano-1-tritylproline tert-butyl ester (2j). The diastereomers
were inseparable on silica gel column. Therefore NMR data for
major diastereomer is provided.
For preparation see general procedure for electrochemical
cyantion (undivided cell).
=
dC (100 Hz, CDCl3) 205.31 (NCO2), 118.24 (CHC N), 70.70
Anal. Calc. for C29H30N2O2: C, 79.42; H, 6.89; N, 6.39. Found:
C, 79.20; H, 6.94; N, 6.24. nmax/cm-1 (neat): 2978, 2361, 1736, 1595,
1489, 1449, 1366. dH (400 MHz, CDCl3) 7.62 (d, J 7.8, 6H, 3 ¥
o-ArH2), 7.30 (t, J 7.3, 6H, 3 ¥ m-ArH2), 7.21 (t, J 6.8, 3H, 3 ¥
=
(CH2CHC N(N)), 56.06 (CH2CH2N), 53.37 (OCH3), 40.02
(OCH3), 36.17 (CH2CH(CH2)O), 29.99 (CHCH2CH), 28.91
(CHCH2CH2). High Resolution Mass Spectrum [EI(+)]: m/z
calcd for C9H14N2O3 [M]+ 198.1004, found 198.1001.
=
p-ArH), 4.14 (dd, J 5.9, 2.4, 1H, CH2CHC N(N)), 3.91 (dd, J 4.9,
trans-2n. dH (300 MHz, CDCl3) 5.50-5.31 (m, 1H,
CH2CHC N(N)), 4.34-4.12 (m, 1H, CH2CHHN), 3.76 (s,
3H, OCH3), 3.68-3.52 (m, 1H, CH2CHHN), 3.40 (s, 3H,
OCH3), 3.21-3.01 (m, 1H, CH2CH(CH)OCH3), 2.40-2.26 (m, 1H,
CHCHHCH), 2.20-2.11 (m, 1H, CHCHHCH), 1.68-1.51 (m, 1H,
CHCHHCH2), 1.44-1.24 (m, 1H, CHCHHCH2).
3.9, 1H, CH2CHCO2(N)), 1.80-1.68 (m, 2H, CHCH2CH2), 1.59
(s, 9H, C(CH3)3), 1.25-1.18 (m, 2H, CHCH2CH2). dC (100 Hz,
CDCl3) 173.87 (CHCO2), 143.57 (3 ¥ ArC), 129.00 (3 ¥ o-ArC2),
=
=
128.22 (3 ¥ m-ArC2), 126.89 (3 ¥ p-ArC), 121.73 (CHC N),
=
81.50 (NC(ArC)3), 78.82 (CH2CHC N(N)), 65.10 (CH2CHCO2),
53.25 (OC(CH3)3), 30.97 (C(CH3)3), 30.20 (CHCH2CH2), 28.02
(CHCH2CH2).
2-tert-Butoxycarbonyl-1-cyano-3,4-dihydro-1H-isoquinoline (2p).
For preparation see general procedure for electrochemical cya-
nation (undivided cell).
cis-2-Cyano-1-methoxycarbonyl-4-methylpiperidine (2l). For
preparation see general procedure for electrochemical cyanation
(undivided cell).
n
max/cm-1 (neat): 2978, 2936, 2237, 1716, 1795, 11456, 1412,
n
max/cm-1 (neat): 2957, 2874, 2237, 1732, 1469, 1404. dH
1317. dH (400 MHz, CDCl3) 7.35-7.13 (m, 4H, 4 ¥ ArH), 6.14-5.81
=
=
(500 MHz, CDCl3) 5.42-5.13 (m, 1H, CH2CHC N(N)), 4.25-
4.00 (m, 1H, CH2CHHN), 3.75 (s, 3H, OCH3), 3.12-2.95 (m,
1H, CH2CHHN), 1.96-1.85 (m, 2H, CHCH2CH), 1.78-1.65 (m,
1H, CH2(CH2)CHCH3), 1.38 (td, J 13.5, 4.5, 1H, CHCHHCH2),
(m, 1H, CCHC N(N)), 4.30-4.02 (m, 1H, CH2CHHN), 3.50-3.20
(m, 1H, CH2CHHN), 3.00-2.81(m, 2H, CCH2CH2), 1.53 (s, 9H,
OC(CH3)3). dC (100 Hz, CDCl3) 134.00 (NCO2), 129.40 (2 ¥ ArC),
=
128.74 (2 ¥ ArC), 127.15 (2 ¥ ArC), 118.20 (CHC N), 77.21
This journal is
The Royal Society of Chemistry 2009
Org. Biomol. Chem., 2009, 7, 351–356 | 355
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