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found: 296.1651. The enantiomeric purity of the major diastereo-
mer was determined by HPLC analysis (Daicel Chiralpak IC, hexane/
Chiralpak AD-H, hexane/isopropanol 95:5, flow rate=1 mLminÀ1
,
retention times: 17.5 min (minor) and 19.8 min (major)).
isopropanol 90/10, flow rate=0.5 mLminÀ1
, retention times:
(2S,3S)-2-Butyl-3-((4-methoxyphenyl)amino)-7-methyloct-4-yn-1-
10.7 min (minor) and 14.2 min (major)).
ol (4Cj): Prepared according to the general procedure starting
from hexanal 1C (66 mL, 0.55 mmol) and (E)-4-methoxy-N-(5-meth-
ylhex-2-ynylidene)aniline (2j; 108 mg, 0.5 mmol). White solid, yield:
118.8 mg, 75%. m.p. 75–788C; [a]D22 =À170.8 (c=1, 99% ee,
CH2Cl2); 1H NMR (CDCl3, 300 MHz) d=6.87–6.61 (m, 4H), 4.19 (s,
1H), 3.92 (dd, J=11.0, 7.6 Hz, 1H), 3.81 (d, J=3.5 Hz, 1H), 3.76 (s,
3H), 2.06 (dd, J=6.4, 2.0 Hz, 2H), 1.75 (dt, J=13.2, 6.6 Hz, 1H),
1.45–1.23 (m, 8H), 0.92 ppm (d, J=6.5 Hz, 9H); 13C NMR (CDCl3,
75 MHz) d=153.3, 141.0, 116.7, 114.7, 84.1, 79.67, 64.7, 55.8, 51.6,
44.2, 29.7, 28.1, 27.9, 23.0, 21.99, 14.0 ppm; HRMS (ESI): m/z calcd
for C20H32NO2 318.2433; found: 318.2419. The enantiomeric purity
of the major diastereomer was determined by HPLC analysis
(Daicel Chiralpak AD-H, hexane/isopropanol 98:2, flow rate=
(2S,3S)-3-((4-Chlorophenyl)amino)-2-methyldec-4-yn-1-ol (4Ag):
Prepared according to the general procedure starting from propa-
nal 1A (40 mL, 0.55 mmol) and (E)-4-chloro-N-(oct-2-yn-1-ylidene)a-
niline (2g; 116.8 mg, 0.5 mmol). Yellow oil, yield: 121.2 mg, 79%.
[a]D22 =À101.5 (c=1, 99% ee, CH2Cl2); 1H NMR (CDCl3, 300 MHz)
d=7.18–7.08 (m, 2H), 6.71–6.59 (m, 2H), 4.12 (dd, J=4.6, 2.5 Hz,
2H), 3.87 (dd, J=10.8, 8.1 Hz, 1H), 3.72 (dd, J=10.8, 4.1 Hz, 1H),
2.15 (td, J=7.0, 2.1 Hz, 3H), 1.35–1.20 (m, 5H), 1.05 (dd, J=6.9,
2.8 Hz, 3H), 0.92–0.81 ppm (m, 2H); 13C NMR (CDCl3, 75 MHz) d
145.7, 128.9, 122.8, 115.4, 85.1, 78.2, 65.8, 50.5, 39.4, 31.0, 28.5,
22.1, 18.6, 14.0 ppm; HRMS (ESI): m/z calcd for C17H24NOCl
294.8316; found: 294.1633. The enantiomeric purity of the major
diastereomer was determined by HPLC analysis (Daicel Chiralpak IB
hexane/isopropanol 98:2, flow rate=1 mLminÀ1, retention times:
10.3 min (minor) and 14.9 min (major)).
0.5 mLminÀ1
(major)).
, retention times: 48.7 min (minor) and 68.4 min
(2S,3S)-5-Cyclohexyl-2-isopropyl-3-((4-methoxyphenyl)amino)-
pent-4-yn-1-ol (4Dk): Prepared according to the general proce-
dure starting from isovaleraldehyde 1D (59 mL, 0.55 mmol) and (E)-
N-(3-cyclohexylprop- 2-ynylidene)-4-methoxyaniline (2k; 121 mg,
0.5 mmol). Yellow oil, yield: 143.5 mg, 87%. [a]D22 =À60.8 (c=1,
78% ee, CH2Cl2); 1H NMR (CDCl3, 300 MHz) d=6.82–6.77 (m, 2H),
6.74–6.69 (m, 2H), 4.28–4.24 (m, 1H), 3.99 (dd, J=11.3, 8.0 Hz, 1H),
3.88 (dd, J=11.3, 3.3 Hz, 1H), 3.75 (d, J=1.9 Hz, 3H), 1.78–1.68 (m,
3H), 1.52–1.23 (m, 10H), 1.05 (d, J=6.7 Hz, 4H), 1.00 ppm (d, J=
6.7 Hz, 3H); 13C NMR (CDCl3, 75 MHz) d=153.1, 140.9, 116.5, 114.7,
90.1, 79.1, 63.0, 55.8, 50.2, 49.7, 32.7, 29.0, 27.6, 25.9, 24.7, 21.2,
20.4 ppm; HRMS (ESI): m/z calcd for C21H32NO2 330.2433; found:
330.2444. The enantiomeric purity of the major diastereomer was
determined by HPLC analysis (Daicel Chiralpak AS-H, hexane/iso-
propanol 95:5, flow rate=1 mLminÀ1, retention times: 10.7 min
(major) and 16.4 min (minor)).
(2S,3S)-3-((4-Methoxyphenyl)amino)-2-methyldec-4-yn-1-ol
(4Ah): Prepared according to the general procedure starting from
propanal 1A (40 mL, 0.55 mmol) and (E)-4-methoxy-N-(oct-2-yn-1-
ylidene)aniline (2h; 114.6 mg, 0.5 mmol). Yellow oil, yield:
109.1 mg, 72%. [a]D22 =À62.8 (c=1, 99% ee, CH2Cl2); 1H NMR
(CDCl3, 300 MHz) d=6.87–6.62 (m, 4H), 4.16–4.07 (m, 1H), 3.90–
3.83 (m, 1H), 3.75 (d, J=2.8 Hz, 3H), 3.71 (d, J=4.0 Hz, 1H), 2.18–
2.07 (m, 2H), 1.45 (s, 2H), 1.34–1.22 (m, 4H), 1.06 (d, J=7.0 Hz,
2H), 0.98–0.83 ppm (m, 3H); 13C NMR (CDCl3, 75 MHz) d=153.2,
141.0, 116.7, 114.7, 85.2, 78.9, 66.2, 55.7, 52.2, 39.4, 31.0, 28.5, 22.2,
18.7, 14.0, 13.7 ppm; HRMS (ESI): m/z calcd for C18H28NO2 290.2120;
found: 290.2115. The enantiomeric purity of the major diastereo-
mer was determined by HPLC analysis (Daicel Chiralpak IC hexane/
isopropanol 90:10, flow rate=0.5 mLminÀ1
, retention times:
20.1 min (minor) and 24.3 min (major)).
(2S,3S)-2-Benzyl-3-((4-methoxyphenyl)amino)-5-phenylpent-4-
yn-1-ol (4Ba): Prepared according to the general procedure start-
ing from hydrocinnamaldehyde 1B (73 mL, 0.55 mmol) and (E)-4-
methoxy-N-(3-phenylprop-2-ynylidene) aniline (2a; 118 mg,
0.5 mmol). Yellow oil, yield: 163.1 mg, 88%. [a]D22 =À29.4 (c=1,
(S)-2-((S)-3-(3-Chlorophenyl)-1-(phenylamino)prop-2-yn-1-
yl)pent-4-en-1-ol (4Ee): Prepared according to the general proce-
dure starting from 4- pentenal 1E (55 mL, 0.55 mmol) and (E)-N-(3-
(3-chlorophenyl)prop-2-yn-1-ylidene)aniline
(2e;
119.8 mg,
0.5 mmol). Yellow oil, yield: 141.3 mg, 87% ; [a]D22 =À158.4 (c=1,
99% ee, CH2Cl2); 1H NMR (CDCl3, 300 MHz) d=7.38–7.10 (m, 4H),
6.84–6.61 (m, 2H), 5.82 (dd, J=17.2, 7.0 Hz, 1H), 5.23–4.93 (m, 2H),
4.55 (d, J=3.6 Hz, 1H), 4.05–3.84 (m, 1H), 3.71 (d, J=5.9 Hz, 1H),
3.63 (s, 1H), 2.38–2.07 (m, 4H), 1.74–1.58 ppm (m, 1H); 13C NMR
(CDCl3, 75 MHz) d=138.2, 136.9, 135.8, 131.6, 129.9, 129.5, 129.4,
129.3, 128.5, 118.7, 117.5, 116.7, 115.2, 114.3, 113.6, 89.1, 83.4, 64.1,
63.8, 54.5, 49.3, 44.0, 42.9, 33.2, 31.9, 31.2, 30.9 ppm; HRMS (ESI):
m/z calcd for C20H21ClNO 3326.1312 found: 326.1321. The enantio-
meric purity of the major diastereomer was determined by HPLC
analysis (Daicel Chiralpak OD-H, hexane/isopropanol 98:2, flow
rate=0.5 mLminÀ1, retention times: 31.0 min (minor) and 36.6 min
(major)).
1
99% ee, CH2Cl2); H NMR (CDCl3, 300 MHz) d=7.45–7.17 (m, 10H),
6.78 (d, J=9.1 Hz, 2H), 6.66 (d, J=9.1 Hz, 2H), 4.38 (d, J=3.8 Hz,
1H), 4.01 (dd, J=11.0, 7.6 Hz, 1H), 3.93–3.84 (m, 1H), 3.75 (s, 3H),
2.96–2.67 ppm (m, 3H); 13C NMR (CDCl3, 75 MHz) d=153.1, 140.6,
139.6, 131.7, 129.1, 128.5, 128.2, 126.3, 116.4, 114.7, 87.9, 85.2, 63.9,
55.6, 50.7, 46.1, 34.7 ppm; HRMS (ESI): m/z calcd for C25H26NO2
372.1964; found: 372.1971. The enantiomeric purity of the major
diastereomer was determined by HPLC analysis (Daicel Chiralpak IA
hexane/isopropanol/ethanol 95:2:3, flow rate=1 mLminÀ1, reten-
tion times: 26.0 min (major) and 38.3 min (minor).
(2S,3S)-2-Benzyl-3-((4-methoxyphenyl)amino)-5-(thiophen-3-
yl)pent-4-yn-1-ol (4Bl): Prepared according to the general proce-
dure starting from hydrocinnamaldehyde 1B (73 mL, 0.55 mmol)
and (E)-4-methoxy-N-(3-(thiophen-3-yl)prop-2-yn-1-ylidene)aniline
(2l, 105.6 mg, 0.5 mmol). Yellow oil, yield: 131.8 mg, 76% yield.
(S)-2-((S)-3-(3-Chlorophenyl)-1-(o-tolylamino)prop-2-yn-1-yl)pent-
4-en-1-ol (4Ef): Prepared according to the general procedure start-
ing from 4-pentenal 1E (55 mL, 0.55 mmol) and (E)-N-(3-(3-chloro-
1
[a]D22 =À2.9 (c=1, 98% ee, CH2Cl2); H NMR (CDCl3, 300 MHz) d=
phenyl)prop-2-yn-1-ylidene)-2-methylaniline
(2 f;
126.8 mg,
7.33–7.01 (m, 11 H), 6.67 (t, J=7.8 Hz, 1H), 6.39 (d, J=9.5 Hz, 2H),
3.72–3.64 (m, 2H), 3.55 (d, J=5.5 Hz, 1H), 2.91–2.76 (m, 1H), 2.75–
2.53 (m, 3H), 2.16 (d, J=11.9 Hz, 1H), 2.07–1.79 ppm (m, 3H);
13C NMR (CDCl3, 75 MHz) d=147.8, 141.9, 140.2, 129.6, 129.2, 128.7,
128.6, 126.7, 126.1, 126.0, 117.6, 113.6, 63.7, 62.5, 53.5, 45.2, 34.3,
33.8, 33.8, 33.1, 32.2, 31.0, 29.8 ppm; HRMS (ESI): m/z calcd for
C22H21NOS 347.4760; found: 347.0307. The enantiomeric purity of
the major diastereomer was determined by HPLC analysis (Daicel
0.5 mmol). Yellow oil, yield: 140.6 mg, 83%; [a]D22 =À125.8 (c=1,
99% ee, CH2Cl2); 1H NMR (CDCl3, 300 MHz) d=7.42–7.03 (m, 4H),
6.89–6.63 (m, 2H), 5.97–5.75 (m, 1H), 5.34–4.96 (m, 2H), 4.57 (d,
J=3.1 Hz, 1H), 4.05 (s, 1H), 3.91 (d, J=3.2 Hz, 1H), 3.71 (d, J=
6.0 Hz, 1H), 2.37–2.22 (m, 2H), 2.15 ppm (d, J=10.1 Hz, 3H);
13C NMR (CDCl3, 75 MHz) d=144.8, 138.2, 136.9, 135.8, 131.6, 130.4,
130.2, 129.9, 129.5, 128.5, 127.2, 127.0, 123.3, 118.1, 117.5, 116.9,
116.7, 115.2, 111.4, 110.4, 89.3, 83.3, 64.3, 63.8, 54.0, 49.2, 44.0, 42.7,
Chem. Eur. J. 2016, 22, 7229 – 7237
7234
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim