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X.-X. Guo et al. / Tetrahedron: Asymmetry 21 (2010) 1730–1736
4.4.4. (1S,2R)-6-Fluoro-2-(4-(triphenylsilyl)but-1-en-3-yn-2-yl)
indan-1-ol 3dm
The enantiomeric excess was measured by HPLC (Chiralpak AD–H
column, 0.5 mL/min, hexane/2-propanol = 9/1, 254 nm, t1 = 26.6 min
4.4.8. (1S,2R)-2-(4-Phenylbut-1-en-3-yn-2-yl)indan-1-ol 3ap
The enantiomeric excess was measured by HPLC (Chiralpak AD–H
column, 0.5 mL/min, hexane/2-propanol = 9/1, 254 nm, t1 = 19.4 min
(1R,2S), t2 = 33.4 min (1S,2R)). ½a D20
¼ ꢁ33 (c 0.93, CHCl3) for 98% ee.
ꢂ
(1R,2S), t2 = 30.5 min (1S,2R)). ½a D20
ꢂ
¼ ꢁ35 (c 0.74, CHCl3) for 99% ee.
1H NMR (CDCl3) d 2.08 (d, J = 6.7 Hz, 1H), 3.07 (dd, J = 15.5, 7.3 Hz,
1H), 3.28 (dd, J = 15.5, 7.3 Hz, 1H), 3.35 (td, J = 7.3, 6.4 Hz, 1H), 5.31
(dd, J = 6.7, 6.4 Hz, 1H), 5.54 (s, 1H), 5.70 (s, 1H), 7.22–7.32 (m, 8H),
7.45 (d, J = 7.3 Hz, 1H); 13C NMR (CDCl3) d 34.5, 51.7, 77.0, 88.9,
91.1, 122.8, 124.0, 124.9, 125.0, 127.1, 128.4, 128.5, 128.8, 130.0,
131.8, 142.7, 143.8. HRMS (ESI) calcd for C19H16NaO (M+Na)+
283.1093, found 283.1090.
1H NMR (CDCl3) d 2.08 (d, J = 6.7 Hz, 1H), 2.98 (dd, J = 15.6, 7.7 Hz,
1H), 3.18 (dd, J = 15.6, 7.0 Hz, 1H), 3.34 (ddd, J = 7.7, 7.0, 6.2 Hz, 1H),
5.20 (br t, J = 6.2 Hz, 1H), 5.58 (s, 1H), 5.81 (s, 1H), 6.86 (ddd, J = 8.8,
8.4, 2.4 Hz, 1H), 7.05 (dd, J = 8.4, 2.6 Hz, 1H), 7.08 (dd, J = 8.4, 5.0 Hz,
1H), 7.32–7.44 (m, 9H), 7.52–7.60 (m, 6H); 13C NMR (CDCl3) d 33.8,
51.7, 76.7 (d, JF–C = 2.1 Hz), 91.3, 108.9, 111.9 (d, JF–C = 22.2 Hz),
115.9 (d, JF–C = 22.2 Hz), 125.9 (d, JF–C = 8.8 Hz), 126.5, 128.1, 129.5,
130.1, 133.3, 135.6, 137.7 (d, JF–C = 2.6 Hz), 145.5 (d, JF–C = 7.2 Hz),
162.3 (d, JF–C = 243.9 Hz). HRMS (ESI) calcd for C31H25FNaOSi
(M+Na)+ 483.1551, found 483.1553.
4.4.9. (1S,2R)-2-(4-(4-Methoxyphenyl)but-1-en-3-yn-2-yl)indan-
1-ol 3aq
The enantiomeric excess was measured by HPLC (Chiralpak AD–H
column, 0.5 mL/min, hexane/2-propanol = 9/1, 254 nm, t1 = 27.9 min
(1R,2S), t2 = 43.5 min (1S,2R)). ½a D20
¼ ꢁ58 (c 0.65, CHCl3) for 99% ee.
ꢂ
4.4.5. 2-Methyl-2-(4-(triphenylsilyl)but-1-en-3-yn-2-yl)indan-
1-ol 3em
1H NMR (CDCl3) d 2.11 (d, J = 6.6 Hz, 1H), 3.07 (dd, J = 15.5, 7.4 Hz,
1H), 3.27 (dd, J = 15.5, 7.4 Hz, 1H), 3.34 (td, J = 7.4, 6.2 Hz, 1H), 3.79
(s, 3H), 5.31 (dd, J = 6.6, 6.2 Hz, 1H), 5.50 (s, 1H), 5.66 (s, 1H), 6.79
(d, J = 8.9 Hz, 2H), 7.18–7.32 (m, 5H), 7.46 (d, J = 7.2 Hz, 1H); 13C
NMR (CDCl3) d 34.6, 51.8, 55.4, 77.1, 87.6, 91.3, 114.0, 114.9, 123.2,
124.9, 125.0, 127.0, 128.8, 130.1, 133.3, 142.8, 143.9, 159.9. Anal.
Calcd for C20H18O2: C, 82.73; H, 6.25. Found: C, 82.71; H, 6.30.
Compound 3em and its trans-isomer trans-3emwereseparatedby
preparative TLC (silica gel, CHCl3). Compound 3em (cis-isomer): The
enantiomeric excess was measured by HPLC (Chiralpak AD–H col-
umn, 0.5 mL/min, hexane/2-propanol = 9/1, 254 nm, t1 = 15.1 min
(1R,2S), t2 = 33.7 min (1S,2R)). ½a D20
¼ ꢁ32 (c 0.70, CHCl3) for 81% ee.
ꢂ
1H NMR (CDCl3) d 1.26 (s, 3H), 2.20 (d, J = 5.2 Hz, 1H), 2.69 (d,
J = 15.4 Hz, 1H), 3.47 (d, J = 15.4 Hz, 1H), 4.82 (d, J = 5.2 Hz, 1H), 5.59
(s, 1H), 5.81 (s, 1H), 7.15–7.25 (m, 4H), 7.32–7.45 (m, 9H), 7.58–
7.67 (m, 6H); 13C NMR (CDCl3) d 25.9, 41.3, 53.1, 82.7, 91.0, 109.2,
124.6, 125.3, 125.8, 127.0, 128.2, 128.9, 130.1, 133.5, 135.4, 135.6,
142.7, 142.9. HRMS (ESI) calcd for C32H28NaOSi (M+Na)+ 479.1802,
found 479.1800. Compound trans-3em: The enantiomeric excess
was measured by HPLC (Chiralpak AD–H column, 0.5 mL/min, hex-
ane/2-propanol = 9/1, 254 nm, t1 = 10.7 min (minor), t2 = 12.2 min
4.4.10. (1S,2R)-2-(4-(Naphthalen-1-yl)but-1-en-3-yn-2-yl)indan-
1-ol 3ar
The enantiomeric excess was measured by HPLC (Chiralpak AD–H
column, 0.5 mL/min, hexane/2-propanol = 9/1, 254 nm, t1 = 21.7 min
(1R,2S), t2 = 32.3 min (1S,2R)). ½a D20
¼ ꢁ65 (c 0.80, CHCl3) for 98% ee.
ꢂ
1H NMR (CDCl3) d 2.10 (d, J = 6.5 Hz, 1H), 3.15 (dd, J = 15.5, 7.5 Hz,
1H), 3.38 (dd, J = 15.5, 7.6 Hz, 1H), 3.46 (ddd, J = 7.6, 7.5, 6.3 Hz, 1H),
5.39 (dd, J = 6.5, 6.3 Hz, 1H), 5.62 (d, J = 1.3 Hz, 1H), 5.85 (d,
J = 0.8 Hz, 1H), 7.27–7.34 (m, 3H), 7.38 (dd, J = 8.2, 7.2 Hz, 1H),
7.47–7.55 (m, 4H), 7.79–7.82 (m, 2H), 8.07–8.12 (m, 1H); 13C NMR
(CDCl3) d 34.6, 51.6, 77.1, 89.1, 93.8, 120.5, 124.3, 125.0, 125.2,
125.3, 126.2, 126.5, 127.0, 127.1, 128.4, 128.9, 129.0, 130.2, 130.9,
133.23, 133.24, 142.7, 143.8. HRMS (ESI) calcd for C23H18NaO
(M+Na)+ 333.1250, found 333.1251.
(major)). ½a 2D0
ꢂ
¼ þ9 (c 0.98, CHCl3) for 43% ee. 1H NMR (CDCl3) d
1.18 (s, 3H), 2.05 (d, J = 6.7 Hz, 1H), 2.77 (d, J = 15.4 Hz, 1H), 3.34 (d,
J = 15.4 Hz, 1H), 5.41 (d, J = 6.3 Hz, 1H), 5.60 (d, J = 1.0 Hz, 1H), 5.73
(d, J = 1.0 Hz, 1H), 7.15–7.26 (m, 3H), 7.30–7.42 (m, 10H), 7.59–7.63
(m, 6H); 13C NMR (CDCl3) d 19.1, 43.0, 53.7, 81.1, 91.5, 109.5, 123.0,
124.2, 124.9, 126.9, 128.1, 128.2, 130.1, 133.5, 135.6, 137.6, 139.8,
143.3. HRMS (ESI) calcd for C32H28NaOSi (M+Na)+ 479.1802, found
479.1802.
4.4.11. 2-(4-(Triphenylsilyl)but-3-yn-2-yl)indan-1-one 3am0
A major isomer (Table 1, entry 2): The enantiomeric excess was
measured by HPLC (Chiralcel OD–H column ꢃ 2, 0.5 mL/min, hex-
ane/2-propanol = 9/1, 254 nm, t1 = 22.9 min (major), t2 = 25.8 min
4.4.6. (1S,2R)-2-(4-(Triisopropylsilyl)but-1-en-3-yn-2-yl)indan-
1-ol 3an
(minor)). ½a 2D0
ꢂ
¼ þ27 (c 1.00, CHCl3) for 63% ee. 1H NMR (CDCl3)
The enantiomeric excess was measured by HPLC (Chiralpak AD–H
column, 0.5 mL/min, hexane/2-propanol = 95/5, 254 nm, t1 =
d 1.43 (d, J = 7.1 Hz, 3H), 2.72 (dt, J = 7.7, 4.0 Hz, 1H), 3.25 (dd,
J = 17.3, 7.7 Hz, 1H), 3.31 (dd, J = 17.3, 4.2 Hz, 1H), 3.49 (qd,
J = 7.1, 4.0 Hz, 1H), 7.20–7.42 (m, 17H), 7.54 (t, J = 7.6 Hz, 1H),
7.75 (d, J = 7.7 Hz, 1H); 13C NMR (CDCl3) d 20.1, 28.9, 29.4, 51.9,
81.4, 112.2, 124.2, 126.6, 127.5, 127.9, 129.7, 133.8, 135.0, 135.4,
137.0, 154.4, 206.7. HRMS (ESI) calcd for C31H26NaOSi (M+Na)+
465.1645, found 465.1640. A minor isomer: The enantiomeric ex-
cess was measured by HPLC (Chiralcel OD–H column ꢃ 2, 0.5 mL/
min, hexane/2-propanol = 9/1, 254 nm, t1 = 20.9 min (major),
14.1 min (1R,2S), t2 = 16.2 min (1S,2R)). ½a D20
¼ ꢁ55 (c 0.80, CHCl3)
ꢂ
for 98% ee. 1H NMR (CDCl3) d 0.97–1.12 (m, 21H), 2.16 (d, J = 6.1 Hz,
1H), 2.96–3.05 (m, 1H), 3.20–3.28 (m, 2H), 5.24 (t, J = 5.7 Hz, 1H),
5.50 (s, 1H), 5.68 (s, 1H), 7.19–7.29 (m, 3H), 7.44 (d, J = 7.3 Hz, 1H);
13C NMR (CDCl3) d 11.3, 18.7, 34.2, 51.2, 76.9, 92.4, 106.7, 124.7,
124.9, 125.3, 127.0, 128.9, 130.1, 142.8, 143.6. HRMS (ESI) calcd for
C
22H32NaOSi (M+Na)+ 363.2115, found 363.2116.
t2 = 21.8 min (minor)). ½a D20
ꢂ
¼ ꢁ58 (c 0.90, CHCl3) for 66% ee. 1H
4.4.7. (1S,2R)-2-(5-(Methoxymethoxy)-5,5-diphenylpent-1-en-
3-yn-2-yl)indan-1-ol 3ao
NMR (CDCl3) d 1.20 (d, J = 7.0 Hz, 3H), 3.05 (dt, J = 8.3, 4.0 Hz,
1H), 3.20 (dd, J = 17.6, 4.0 Hz, 1H), 3.34 (dd, J = 17.6, 8.3 Hz, 1H),
3.43 (qd, J = 7.0, 4.0 Hz, 1H), 7.20–7.44 (m, 11H), 7.46 (d,
J = 7.6 Hz, 1H), 7.54–7.60 (m, 6H), 7.73 (d, J = 7.5 Hz, 1H); 13C
NMR (CDCl3) d 15.9, 28.2, 29.7, 50.7, 80.6, 114.4, 124.0, 126.7,
127.6, 128.0, 129.9, 134.0, 135.0, 135.6, 137.5, 154.2, 206.2. HRMS
(ESI) calcd for C31H26NaOSi (M+Na)+ 465.1645, found 465.1647.
The enantiomeric excess was measured by HPLC (Chiralpak AD–
H
column, 0.5 mL/min, hexane/2-propanol = 9/1, 254 nm,
t1 = 17.6 min (1R,2S), t2 = 29.6 min (1S,2R)). ½a D20
¼ ꢁ20 (c 0.94,
ꢂ
CHCl3) for 95% ee. 1H NMR (CDCl3) d 2.98–3.07 (m, 1H), 3.24–
3.32 (m, 3H), 3.27 (s, 3H), 4.67 (d, J = 7.1 Hz, 1H), 4.80 (d,
J = 7.1 Hz, 1H), 5.21 (dd, J = 8.2, 6.4 Hz, 1H), 5.52 (s, 1H), 5.68 (s,
1H), 7.18–7.32 (m, 9H), 7.40–7.44 (m, 3H), 7.48–7.52 (m, 2H);
13C NMR (CDCl3) d 34.7, 51.1, 56.0, 77.3, 80.0, 89.0, 90.2, 93.5,
124.4, 124.8, 125.4, 126.8, 126.9, 127.0, 127.8, 127.9, 128.28,
128.32, 128.7, 130.2, 142.5, 143.6, 143.9, 144.0. HRMS (ESI) calcd
for C28H26NaO3 (M+Na)+ 433.1774, found 433.1771.
4.5. Transformation of compound 3am into 4
To a solution of 3am (132.8 mg, 0.30 mmol, 99% ee) in THF (6 mL)
was added tetrabutylammonium fluoride (TBAF) solution (0.30 mL,