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M. E. Krafft et al. / Tetrahedron Letters 46 (2005) 6359–6362
(dd, 1H, J = 17.6, 1.5, CH@CHH), 5.84 (ddt, 1H, J = 16.9,
(dm, 1H, C@CHH), 7.29 (d, 2H, J = 7.8, aromatics), 7.71
(d, 2H, J = 7.8, aromatics).
Compound 31: 500 MHz H NMR: d 1.60–1.65 (m, 1H,
10.3, 6.6, CH2CH@CH2), 6.00 (s, 1H, C@CHH), 6.02 (d,
J = 1.5, 1H, C@CHH).
1
1
Compound 20: 500 MHz H NMR: d 1.41–1.50 (m, 2H,
CH2CHHCH2), 1.75–1.86 (m, 3H, CH2CHHCH2,
CHCH2CH2), 2.14–2.19 (m, 1H, CH2CHHCH@C), 2.28
(ddt, 1H, J = 20, 4.9, 4.9, CH2CHHCH@C), 3.79 (s, 3H,
OCH3), 4.56 (broad t, 1H, J = 5, CH2CHOHC@C), 7.13
(t, 1H, J = 4, CH2CH@C).
CH2CH2CH2CH@C), 1.64–1.80 (m, 4H, CHO-
HCH2CH2CH2, CH2CH2CHOH), 2.07 (dt, 2H, J = 7.3,
7.3, CH2CH2CH@C), 4.39 (dd, 1H, J = 7.3, 5.1,
CH2CHOHC@C), 4.95 (partially obscured dt, 1H,
J = 10.3, 2.2, CH@CHH), 5.01 (dq, 1H, J = 16.9, 1.5,
CH@CHH), 5.8 (ddt, 1H, J = 16.6, 6.6, 7.6,
CH2CH@CH2), 5.98 (s, 1H, C@CHH), 6.0 (d, 1H,
J = 1.5, C@CHH).
1
Compound 32: 500 MHz H NMR: d 1.54–1.64 (m, 2H,
CHOHCH2CH2CH2), 1.70–1.88 (m, 4H, CH2CH2-
CH2CH@C, CHOHCH2CH2), 2.03–2.16 (m, 1H, CH2CH-
HCH@C), 2.26 (ddt, 1H, J = 20.4, 4.2, 4.2,
CH2CHHCH@C), 3.75 (s, 3H, OCH3), 4.53 (m, 1H,
CH2CHOHC), 7.09 (t, 1H, J = 3.6, CH2CH@C).
1
Compound 21: 500 MHz H NMR: d 1.65–1.72 (m, 2H,
CHCH2CH2), 2.16 (m, 2H, CH2CH2CH@C), 2.36 (s, 3H,
CCH3), 4.45 (t, 1H, J = 7, 6, CH2CHC@C), 4.97 (d, 1H,
J = 10, CH@CHH), 5.04 (d, 1H, J = 17, CH@CHH), 5.82
(ddt, 1H, J = 17.1, 9.3, 6.4, CH2CH@CH2), 6.02 (s, 1H,
C@CHH), 6.11 (s, 1H, C@CHH).
Compound 35: 500 MHz 1H NMR: d 1.43–1.51 (m, 1H, m,
1H, CH2CHHCH2CH@C), 1.63–1.71 (m, 2H, CHO-
HCH2CH2CH2), 1.74–1.82 (m, 1H, CHOHCHHCH2),
1.89–1.94 (m, 1H, CHOHCHHCH2), 1.96–2.03 (m, 1H,
CH2CHHCH2CH@C), 2.22 (m, 1H, CH2CHHCH@C),
2.42 (ddt, 1H, J = 16.1, 9.5, 2.2, CH2CHHCH@C), 4.48 (d,
1H, J = 9.5, CH2CHOHC), 6.81 (dt, 1H, J = 6.8, 1.7
CH2CH@C).
Compound 22: 500 MHz 1H NMR: d 0.99 (s, 3H, CCH3),
1.00 (s, 3H, CCH3), 2.06 (dd, 1H, J = 13.7, 7.3,
CCH2CH@C), 2.24 (dd, 1H, J = 13.7, 7.8, CCH2CH@C),
4.06 (s, 1H, CCHC@C), 5.12 (d, 1H, J = 17.7, CH@CHH),
5.13 (d, 1H, J = 10.8, CH@CHH), 5.87 (ddt, 1H, J = 16.1,
10.7, 7.3, CH2CH@CH2), 5.99 (s, 1H, C@CHH), 6.14 (s,
1H, C@CHH).
Compound 37: 500 MHz 1H NMR: d 1.08 (s, 3H, CH3C),
1.11 (s, 3H, CH3C), 2.28 (ddd, 2H, J = 18.6, 3.0, 1.2,
CCHHCH@C),
2.44
(dd,
J = 18.6,
2.4,
2.4,
1
Compound 24: 500 MHz H NMR: d 1.13–1.75 (m, 9H,
CCHHCH@C), 4.38 (broad s, 1H, CCHOHC@), 6.77 (t,
1H, J = 4, CH2CH@C).
CH2CH2CH2, CH2CH2CH2, CH2CH2CH2, CH2CH2CH2,
CH2CHCHCH), 2.14 (m, 1H, CH2CHCHCH@), 3.78 (s,
3H, OCH3), 4.81 (d, 1H, J = 1, CHCHC@), 5.06 (dd, 1H,
J = 10.3, 2.0, CH@CHH), 5.14 (dd, 1H, J = 17.1, 1.5,
CH@CHH), 5.76 (ddd, 1H, J = 16.6, 9.5, 9.8,
CHCH@CH), 5.88 (dd, 1H, J = 1.5, 1.5, C@CHH), 6.35
(s, 1H, J = 1.5, 1.5, C@CHH).
1
Compound 39: 500 MHz H NMR: d 1.25–1.36 (m, 4H,
CHOHCHCH2CH2, CHOHCHCH2CH2CH2), 1.59–1.60
(m, 1H, CHOHCHCH2CH2), 1.81–1.84 (m, 2H, CH2CH2-
CH2CHCH@C), 1.99–2.04 (m, 2H, CH2CH2CHCH@C),
2.11–2.13 (m, 1H, CH2CHCH@C), 3.78 (s, 3H, OCH3),
4.60 (d, 1H, J = 8.5, CHCHC@C), 6.85 (broad s, 1H,
CHCH@C).
Compound 25: 500 MHz 1H NMR: d 3.79 (s, 3H, OCH3),
5.33 (dd, 1H, J = 10.8, 1.5, CH@CHH), 5.60 (t, 1H, J = 1,
ArCHC), 5.66 (dd, J = 17.3, 1.5, CH@CHH), 5.92 (s, 1H,
C@CHH), 6.37 (s, 1H, C@CHH), 6.94 (dd, 1H, J = 17.3,
11.2, ArCH@CH2), 7.33 (dd, 2H, J = 4.6, 4.9, aromatics),
7.47 (dd, 1H, J = 4.6, 4.4, aromatics), 7.52 (dd, 1H,
J = 4.7, 4.9, aromatics).
Compound 40: 500 MHz 1H NMR: d 3.90 (s, 3H,
O@COCH3), 5.45 (s, 1H, ArCHOHC), 7.53–7.46 (m, 3H,
aromatics), 7.59 (s, 1H, ArCH@C), 7.63 (d, 1H, J = 6.3,
aromatics).
Compound 41: 500 MHz 1H NMR: d 1.00 (d, 3H, J = 6.6,
CHCH3), 1.35 (ddd, 1H, J = 14.6, 4.2, 12.6,
CHCHHCHOH), 1.74 (dddd, 1H, J = 19, 10.2, 2.4, 1.2,
CHCHHCH@C), 1.91–2.03 (m, 2H, CH2CHCH3CH2,
CHCHHCHOH), 2.36 (dddd, 1H, J = 19.2, 6.0, 5.4, 1.2,
CHCHHCH@C), 3.77 (s, 3H, OCH3), 4.56 (broad m, 1H,
CH2CHOHC@C), 7.09 (dd, 1H, J = 5.4, 2.4, CH2CH@C).
Compound 42: 500 MHz 1H NMR: d 0.91 (s, 3H, CH3C),
1.04 (s, 3H, CH3C), 1.51 (dd, 1H, J = 13.2, 8.4,
CCHHCHOH), 1.83 (ddd, 1H, J = 13.2, 6.3, 2.1,
CCHHCHOH), 2.0 (dddd, 1H, J = 19.2, 4.9, 1.7, 1.7,
CCHHCH@C), 2.11 (ddd, 1H, J = 19.5, 3.0, 3.1,
CCHHCH@C), 3.78 (s. 3H, OCH3), 4.57 (m, 1H,
CH2CHOHC@C), 7.00 (ddd, 1H, J = 4.9, 3.8, 1.1,
CH2CH@C).
Compound 27: 500 MHz 1H NMR: d 0.98 (s, 3H, CCH3),
1.00 (s, 3H, CCH3), 1.51 (dd, 1H, J = 14.8, 2.8, CCHH-
CHOH), 1.57 (dd, 1H, J = 14.6, 8.7, CCHHCHOH), 2.05
(dd, 1H, J = 13.1, 6.3, CCHHCH@CH2), 2.10 (dd, 1H,
J = 13.1, 6.3, CCHHCH@CH2), 3.78 (s, 3H, OCH3), 4.59
(dd, 1H, J = 8.4, 2.8, CH2CHC@C), 5.02 (dm, 1H,
J = 16.7, CH@CHH), 5.03 (dm, 1H, J = 10.1, CH@CHH),
5.80 (obscured s, 1H, C@CHH), 5.84 (ddt, 1H, J = 16.7,
10.4, 7.3, CH2CH@CH2), 6.18 (s, 1H, C@CHH).
Compound 28: 500 MHz 1H NMR: d 2.45 (s, 3H, ArCH3),
3.25 (dd, 1H, J = 14.5, 7.8, TsNCHHCHOHC@C), 3.35
(dd, 1H, J = 14.5, 3.4, TsNCHHCHOHC@C), 3.75 (s, 3H,
OCH3), 3.91 (dd, 2H, J = 4.0, 6.0, TsNCH2CH@C), 4.69
(dd, 1H, J = 7.6, 3.9, CH2CHOHC@C), 5.18 (dm, 1H,
J = 10, CH@CHH), 5.21 (dm, 1H, J = 15.4, CH@CHH),
5.68 (ddt, 1H, J = 17.1, 9.8, 6.3, CH2CH@CH2), 6.11 (t,
1H, J = 1.8, C@CHH), 6.39 (t, 1H, J = 1.2, C@CHH),
7.32 (d, 2H, J = 13, aromatics), 7.73 (d, 2H, J = 13.5,
aromatics).
Compound 43: 500 MHz 1H NMR: d 2.45 (s, 3H, ArCH3),
3.15 (dd, 1H, J = 12, 4.4, TsNCHHCHOH), 3.41 (dd, 1H,
J = 12.2, 4.9, TsNCHHCHOH), 3.62 (broad d, 1H, J = 19,
TsNCHHCH@C), 3.79 (s, 3H, OCH3), 3.91 (d, 1H,
J = 3.4, TsNCHHCH@C), 4.63 (broad s, 1H,
CH2CHOHC@C), 6.94 (t, 1H, J = 3.5, CH2CH@C), 7.35
(d, 2H, J = 8, aromatics), 7.71 (d, 2H, J = 7, aromatics).
Compound 44: 500 MHz 1H NMR: d 0.87 (d, 3H, J = 4.5,
CH3CH), 2.43 (s, 3H, ArCH3), 3.69 (dd, 1H, J = 20, 1.5,
TsNCHHCH@C, TsNCHCH3CHOHC@C), 3.80 (s,
3H, OCH3), 4.28–4.37 (m, 3H, CHCHOHC@C,
TsNCHCH3CHOHC@C, TsNCHHCH@C), 7.02 (m,
1H, CH2CH@C), 7.32 (d, 2H, J = 8, aromatics), 7.78 (d,
2H, J = 7.5, aromatics).
Compound 29: 500 MHz 1H NMR: d 1.08 (d, 3H, J = 6.8,
CH3CH), 2.44, (s, 3H, ArCH3), 3.70 (dd, 1H, J = 16.2, 8.4,
TsNCHHCH@CH2), 3.83 (s, 3H, OCH3), 3.97 (ddt, 1H,
J = 16.2, 5.4, 1.8, TsNCHHCH@CH2), 4.09 (qd, 1H,
J = 6.8, 6.8, TsNCHCH3CH), 4.50 (d, 1H, J = 5.9,
CHCHOHC), 5.14 (dm, 1H, J = 10.3, CH@CHH), 5.21
(dm, 1H, J = 17.1, CH@CHH), 5.81 (ddt, 1H, J = 17.1,
10.3, 7.8, CH2CH@CH2), 5.93 (dm, 1H, C@CHH), 6.38