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X.-F. Yang et al. / Tetrahedron: Asymmetry 18 (2007) 2668–2673
1H). 13C NMR (100 MHz, CDCl3): d 135.5, 133.8, 131.9,
129.6, 129.4, 128.9, 128.3, 125.1, 121.9, 86.9, 86.5, 61.9.
8H), 6.04 (s, 1H), 2.63 (s, 1H). 13C NMR (100 MHz,
CDCl3): d 137.9, 131.8, 129.8, 129.7, 128.7, 128.5, 128.3,
127.3, 122.3, 87.6, 86.7, 62.5.
4.4.5. (R)-1-(4-Methylphenyl)-3-phenyl-prop-2-yn-1-ol.11a
90% isolated yield. 60% ee as determined by HPLC analysis
(Chiralcel OD-H column, 15% IPA in hexane, 0.5 mL/min,
4.4.11. (R)-1-(4-Bromophenyl)-3-phenyl-prop-2-yn-1-ol.11a
98% isolated yield. 89% ee determined by HPLC analysis
(Chiralcel OD-H column, 20% IPA in hexane, 0.5 mL/
min, 254 nm UV detector). Retention time: tmajor = 14.268
254 nm UV detector). Retention time: tmajor = 16.345 and
23
tminor = 28.673 min. ½aꢁ ¼ þ2:2 (c 0.452, DCM). 1H
D
23
1
NMR (300 MHz, CDCl3) d 7.43–7.37 (m, 4H), 7.24–7.22
(m, 3H), 7.16–7.11 (m, 2H), 5.56 (s, 1H), 2.28 (s, 3H),
2.25 (s, 1H). 13C NMR (100 MHz, CDCl3): d 138.3,
137.8, 131.7, 129.3, 128.5, 128.3, 126.7, 122.5, 88.9, 86.5,
64.9, 21.2.
and tminor = 32.198 min. ½aꢁD ¼ þ3:9 (c 0.568, DCM). H
NMR (300 MHz, CDCl3) d 7.54–7.44 (m, 6H), 7.35–7.19
(m, 3H), 5.65 (s, 1H), 2.44 (br, 1H). 13C NMR
(100 MHz, CDCl3): d 139.6, 131.8, 131.5, 128.8, 128.4,
127.7, 122.4, 122.1, 88.2, 87.0, 64.4.
4.4.6. (R)-1-(3-Methylphenyl)-3-phenyl-prop-2-yn-1-ol.11a
92% isolated yield. 66% ee determined by HPLC analysis
(Chiralcel OD-H column, 20% IPA in hexane, 0.5 mL/
4.4.12. (R)-1-(4-Methoxyphenyl)-3-phenyl-prop-2-yn-1-ol.11a
89% isolated yield. 56% ee determined by HPLC analysis
(OD-H column, 15% IPA in hexane, 0.5 mL/min, 254 nm
min, 254 nm UV detector). Retention time: tmajor = 15.545
UV detector). Retention time: tmajor = 22.093 and
23
and tminor = 28.54 min. ½aꢁ ¼ þ2:8 (c 0.36, DCM). 1H
23
tminor = 42.388 min. ½aꢁ ¼ þ0:9 (c 0.442, DCM). 1H
D
D
NMR (300 MHz, CDCl3) d 7.48–7.41 (m, 4H), 7.40–7.24
(m, 4H), 7.16 (d, J = 7.4 Hz, 1H), 5.65 (d, J = 5.5 Hz,
1H), 2.38 (s, 3H), 2.35 (s, 1H). 13C NMR (100 MHz,
CDCl3): d 140.6, 138.5, 131.8, 129.2, 128.6, 128.3, 127.4,
123.8, 122.5, 88.8, 86.6, 65.2, 21.5.
NMR (300 MHz, CDCl3) d 7.56–7.45 (m, 4H), 7.33–7.25
(m, 3H), 6.95–6.91 (m, 2H), 5.64 (s, 1H), 3.82 (s, 3H),
2.28 (br, 1H). 13C NMR (100 MHz, CDCl3): d 159.8,
133.0, 131.7, 128.6, 128.3, 128.2, 122.5, 114.0, 113.8, 88.9,
86.5, 64.7, 55.4.
4.4.7. (R)-1-(2-Methylphenyl)-3-phenyl-prop-2-yn-1-ol.11a
90% isolated yield. 12% ee as determined by HPLC analysis
(Chiralcel OD-H column, 10% IPA in hexane, 0.5 mL/min,
4.4.13. (R)-1,5-Diphenyl-pent-1-yn-3-ol.3a 79% isolated
yield. 22% ee determined by HPLC analysis (OD-H col-
umn, 10% IPA in hexane, 0.5 mL/min, 254 nm UV detec-
254 nm UV detector). Retention time: tmajor = 19.34 and
tor). Retention time: tmajor = 33.655 and tminor
=
23
tminor = 41.925 min. ½aꢁ ¼ ꢀ3:6 (c 0.436, DCM). 1H
23
70.75 min. ½aꢁD ¼ ꢀ13:9 (c 0.458, CHCl3). 1H NMR
(300 MHz, CDCl3) d 7.45–7.42 (m, 2H), 7.32–7.19 (m,
8H), 4.59 (t, J = 6.6 Hz, 1H), 2.86 (t, J = 7.7 Hz, 2H),
2.16–2.10 (m, 2H), 2.03 (br, 1H). 13C NMR (100 MHz,
CDCl3): d 142.2, 131.6, 129.5, 129.4, 128.4, 128.3, 128.2,
127.0, 124.3, 88.6, 86.5, 62.1, 39.8, 31.8.
D
NMR (300 MHz, CDCl3) d 7.726 (d, J = 3.7 Hz, 1H),
7.708 (d, J = 3.7 Hz, 2H), 7.47–7.17 (m, 6H), 5.82 (s,
1H), 2.48 (s, 3H), 2.31 (s, 1H). 13C NMR (100 MHz,
CDCl3): d 138.4, 136.0, 131.7, 130.8, 128.5, 128.3, 126.9,
126.2, 122.5, 88.5, 86.5, 62.9, 19.0.
4.4.8.
(R)-1-(4-Chlorophenyl)-3-phenyl-prop-2-yn-1-ol.11a
4.4.14. (+)-1,4-Diphenyl-pent-1-yn-3-ol. 87% isolated
yield. 20% ee determined by HPLC analysis (OD-H
column, 20% IPA in hexane, 0.5 mL/min, 254 nm UV
96% isolated yield. 88% ee determined by HPLC analysis
(Chiralcel OD-H column, 20% IPA in hexane, 0.5 mL/
min, 254 nm UV detector). Retention time: tmajor = 13.813
detector). Retention time: tmajor = 15.87 and tminor
=
23
D
and tminor = 29.845 min. ½aꢁ ¼ þ8:5 (c 0.4, DCM). 1H
23
19.08 min. ½aꢁD ¼ þ15:5 (c 1.21, CHCl3). 1H NMR
(300 MHz, CDCl3) d 7.39–7.27 (m, 10H), 4.66 (dd,
J = 6.9 Hz, J = 9.7 Hz, 1H), 3.17–3.09 (m, 1H), 1.46 (dd,
J = 2.6 Hz, J = 4.9 Hz, 3H). 13C NMR (100 MHz, CDCl3):
d 141.9, 131.6, 128.9, 128.6, 128.4, 128.3, 128.2, 127.5,
127.0, 122.6, 88.6, 86.3, 67.9, 46.5, 16.8.
NMR (300 MHz, CDCl3) d 7.54–7.26 (m, 9H), 5.66 (s,
1H), 2.34 (s, 1H). 13C NMR (100 MHz, CDCl3): d 142.9,
139.2, 133.0, 131.7, 128.7, 128.5, 128.3, 128.1, 127.3,
122.2, 88.4, 86.8, 64.2.
4.4.9.
(R)-1-(3-Chlorophenyl)-3-phenyl-prop-2-yn-1-ol.11a
4.4.15. (+)-1,5-Diphenyl-pent-1-en-4-yn-3-ol.3a 85% iso-
lated yield. 36% ee determined by HPLC analysis (OD-H
column, 20% IPA in hexane, 0.5 mL/min, 254 nm UV
96% isolated yield. 89% ee determined by HPLC analysis
(Chiralcel OD-H column, 15% IPA in hexane, 0.5 mL/min,
254 nm UV detector). Retention time: tmajor = 16.135 and
23
1
tminor = 46.14 min. ½aꢁ ¼ þ9:8 (c 0.408, DCM). H NMR
(300 MHz, CDCl3) d D7.53 (s, 1H), 7.39 (s, 3H), 7.24–7.17
(m, 5H), 5.58 (s, 1H), 2.41 (br, 1H). 13C NMR (100 MHz,
CDCl3): d 142.6, 134.5, 131.8, 129.9, 129.7, 128.8, 128.5,
128.4, 127.6, 126.9, 124.9, 122.1, 88.0, 87.1, 64.4.
detector). Retention time: tmajor = 21.775 and tminor
=
23
61.163 min. ½aꢁD ¼ þ0:7 (c 0.722, CHCl3). 1H NMR
(300 MHz, CDCl3) d 7.48–7.20 (m, 10H), 6.82 (d,
J = 15.8 Hz, 1H), 6.41–6.34 (m, 1H), 5.27 (s, 1H), 1.80 (s,
1H).
4.4.10. (ꢀ)-1-(2-Chlorophenyl)-3-phenyl-prop-2-yn-1-ol.11d,e
90% isolated yield. 88% ee determined by HPLC analysis
(Chiralcel OD-H column, 10% IPA in hexane, 0.5 mL/
min, 254 nm UV detector). Retention time: tmajor = 20.955
References
1. (a) Marshall, J. A.; Wang, X. J. J. Org. Chem. 1992, 57, 1242–
1252; (b) Fox, M. E.; Li, C.; Marino, J. P., Jr.; Overman, L.
E. J. Am. Chem. Soc. 1999, 121, 5467–5480; (c) Myers, A. G.;
20
1
and tminor = 24.5 min. ½aꢁD ¼ ꢀ31:9 (c 0.514, DCM). H
NMR (300 MHz, CDCl3) d 7.82 (s, 1H), 7.45–7.31 (m,