Protein Kinase C Translocation
77.7, 73.6, 68.0, 65.5, 56.1, 43.0, 39.0, 38.5, 36.3, 29.2, 28.8,
25.9, 23.9, 21.2, 16.9, 14.5, 10.3 ppm; IR (neat) 3406, 1714,
1630 cm-1; LRMS (ES) 505 (MH-, 100%); HRMS (MALDI)
calcd for C26H34O10Na (MNa+) 529.2050, found 529.2026.
1708, 1626 cm-1; LRMS (ES-neg ion) 553 (M-H, 100); HRMS
(MALDI) calcd for
577.2017.
C
30H34O10Na (MNa+) 577.2044, found
P h or bol 12,13-Diter ep h th a la te (16). Viscous yellow oil;
[R]D +3.6° (c 0.3, MeOH); 1H NMR (400 MHz, CD3OD) δ 8.14-
8.08 (m, 8H), 7.62 (s, 1H), 5.86 (d, J ) 10.3 Hz, 1H), 5.71 (d,
J ) 4.4 Hz, 1H), 3.97 (AB, J ) 13.0 Hz, 2H), 3.46 (t, J ) 5.1
Hz, 1H), 3.25 (t, J ) 2.7 Hz, 1H), 2.59 (d, J ) 19.0 Hz, 1H),
2.53 (d, J ) 19.0 Hz, 1H), 2.48 (dq, J ) 10.3, 6.3 Hz, 1H), 1.75
(d, J ) 1.5 Hz, 3H), 1.48 (s, 3H), 1.40 (d, J ) 5.4 Hz, 1H), 1.31
(s, 3H), 0.98 (d, J ) 6.3 Hz, 3H) ppm; 13C NMR (100 MHz,
CD3OD) δ 210.0, 177.8, 169.0, 168.6, 167.0, 160.2, 142.8, 134.6,
134.5, 134.2, 130.70, 130.66, 130.5, 129.0, 79.9, 79.8, 74.7, 68.1,
68.0, 57.5, 44.8, 40.2, 38.5, 37.6, 28.4, 24.3, 17.8, 15.1, 10.3
ppm; IR (neat) 3405, 1785, 1706 cm-1; HRMS calcd for
P h or bol 12-Ad ip a te-13-a ceta te (11). Clear, pale yellow
oil; [R]D +7.9° (c 0.1, MeOH); 1H NMR (400 MHz, CDCl3) δ
7.58 (br s, 1H), 5.68 (d, J ) 5.1 Hz, 1H), 5.54 (br s, 1H), 5.41
(d, J ) 10.6 Hz, 1H), 4.02 (AB, J ) 13.0 Hz, 2H), 3.26-3.23
(m, 2H), 2.54 (d, J ) 19.8 Hz, 1H), 2.47 (d, J ) 19.6 Hz, 1H),
2.41-2.35 (m, 4H), 2.18-2.11 [m, 2H containing 2.14 (dq, J )
10.6, 6.6 Hz, 1H)], 2.09 (s, 3H), 1.78-1.77 (m, 3H), 1.71-1.69
(br m, 4H), 1.24 (s, 3H), 1.20 (s, 3H), 1.09 (d, J ) 5.1 Hz, 1H),
0.89 (d, J ) 6.2 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ
173.6, 172.9, 160.8, 140.3, 132.7, 128.9, 78.1, 76.5, 73.7, 68.0,
56.2, 42.9, 39.1, 38.6, 36.3, 34.3, 33.1, 25.8, 24.6, 24.1, 23.9,
21.2, 16.9, 14.6, 10.3; IR (neat) 3415, 1712 cm-1; HRMS
C
36H34O12Na [(M - 2H+)Na+] 681.1953, found 681.1926.
C
28H38O10Na (MNa+) 557.2363, found
P h or bol 12,13-Disu ccin a te (17). Clear, yellow oil; [R]D
(MALDI) calcd for
557.2344.
1
+22.0° (c 0.2, MeOH); H NMR (400 MHz, CD3OD) δ 7.56 (s,
1H), 5.62 (d, J ) 4.9 Hz, 1H), 5.44 (d, J ) 10.7 Hz, 1H), 3.94
(AB, J ) 13.2 Hz, 2H), 3.30 (t, J ) 5.4 Hz, 1H), 3.17-3.14 (m,
1H), 2.62-2.60 (m, 8H), 2.54 (d, J ) 19.5 Hz, 1H), 2.48 (d, J
) 19.0 Hz, 1H), 2.23 (dq, J ) 10.5, 6.6 Hz, 1H), 2.03 (s, 1H),
1.74 (dd, J ) 2.9, 1.0 Hz, 3H), 1.26 (s, 3H), 1.22 (s, 3H), 1.15
(d, J ) 5.4 Hz, 1H), 0.90 (d, J ) 6.8 Hz, 3H) ppm; 13C NMR
(100 MHz, CD3OD) δ 210.6, 177.0, 175.9, 174.5, 160.7, 142.9,
134.7, 129.4, 79.9, 78.8, 74.7, 68.0, 67.2, 57.3, 44.3, 39.9, 38.4,
36.9, 30.4, 30.3, 29.9, 29.6, 27.5, 23.9, 17.3, 14.7, 10.1 ppm; IR
P h or bol 12-Seba ca te-13-a ceta te (12). Clear oil; [R]D +3.1°
(c 0.1, CH2Cl2); 1H NMR (400 MHz, CDCl3) δ 7.60 (s, 1H), 5.68
(d, J ) 4.8 Hz, 1H), 5.59 (br s, 1H), 5.40 (d, J ) 10.3 Hz, 1H),
4.02 (AB, J ) 12.8 Hz, 2H), 3.30-3.20 (m, 2H), 2.57 (d, J )
19.0 Hz, 1H), 2.48 (d, J ) 19.0 Hz, 1H), 2.35-2.31 (m, 4H),
2.17 (s, 1H), 2.15 (dq, J ) 10.6, 6.4 Hz, 1H), 2.09 (s, 3H), 1.77
(dd, J ) 2.6, 1.1 Hz, 3H), 1.66-1.58 (m, 4H), 1.67-1.58 (m,
4H), 1.37-1.28 (m, 4H), 1.24 (s, 3H), 1.21 (s, 3H), 1.09 (d, J )
5.1 Hz, 1H), 0.89 (d, J ) 6.2 Hz, 3H) ppm; 13C NMR (100 MHz,
CDCl3) δ 173.6, 173.4, 161,0, 140.4, 132.8, 129.1, 78.3, 76.6,
73.7, 68.0, 65.7, 42.9, 39.1, 38.4, 36.3, 34.6, 33.9, 31.7, 29.13,
29.06, 29.01, 28.99, 25.8, 25.2, 24.7, 23.9, 21.2, 17.0, 14.6, 10.2
ppm; IR (neat) 3410, 1712, 1629 cm-1; HRMS (MALDI) calcd
for C32H46O10Na (MNa+) 613.2989, found 613.2997.
(neat) 3405, 1715 cm-1; HRMS (MALDI) calcd for C28H36O12
Na (MNa+) 587.2099, found 587.2107.
-
P h or bol 12-Aceta te-13-su ccin a te (18). Clear, viscous
1
liquid; [R]D +7.7° (c 0.3, CH2Cl2); H NMR (400 MHz, CDCl3)
δ 7.55 (s, 1H), 5.80 (br s, 1H), 5.64 (d, J ) 4.4 Hz, 1H), 5.33 (d,
J ) 10.3 Hz, 1H), 3.97 (AB, J ) 13.0 Hz, 2H), 3.26-3.22 (m,
2H), 2.84-2.75 (m, 1H), 2.70-2.60 (m, 1H), 2.59-2.48 (m, 4H),
2.19-2.14 [m, 2H containing 2.16 (s, 1H)], 2.09 (br s, 1H), 2.06
(s, 3H), 1.73 (d, J ) 1.5 Hz, 3H), 1.23 (s, 3H), 1.22 (s, 3H),
1.07 (d, J ) 4.9 Hz, 1H), 0.86 (d, J ) 6.3 Hz, 3H) ppm; 13C
NMR (100 MHz, CDCl3) δ 209.7, 176.0, 175.2, 170.9, 161.0,
140.7, 132.9, 128.4, 78.6, 76.9, 73.7, 67.3, 66.0, 55.9, 42.8, 38.8,
38.2, 36.1, 29.1, 28.6, 26.2, 23.8, 21.2, 17.0, 14.6, 10.3 ppm; IR
(neat) 3401, 1725, 1629 cm-1; HRMS (MALDI) calcd for
P h or bol 12-Tetr a d eca d ioa te-13-a ceta te (13). Yellow oil;
[R]D +5.4° (c 0.25, CH2Cl2); 1H NMR (400 MHz, CDCl3) δ 7.63-
7.60 (m, 1H), 5.67 (d, J ) 4.4 Hz, 1H), 5.61 (br s, 1H), 5.40 (d,
J ) 10.3 Hz, 1H), 4.01 (AB, J ) 12.8 Hz, 2H), 3.30-3.24 (m,
2H), 2.58 (d, J ) 19.0 Hz, 1H), 2.48 (d, J ) 19.0 Hz, 1H), 2.36-
2.31 (m, 4H), 2.172 (s, 1H), 2.167 (dq, J ) 10.3, 6.6 Hz, 1H),
2.09 (s, 3H), 1.77-1.76 (m, 3H), 1.67-1.57 (m, 4H), 1.35-1.22
(m, 19H), 1.21 (s, 3H), 1.08 (d, J ) 5.1 Hz, 1H), 0.89 (d, J )
6.6 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ 210.0, 173.93,
173.85, 161.5, 140.6, 133.0, 129.3, 78.3, 76.6, 73.7, 68.0, 65.6,
56.1, 42.8, 38.9, 38.3, 36.1, 34.6, 29.4, 29.3, 29.2, 29.13, 29.08,
29.04, 28.9, 28.8, 25.6, 25.0, 24.5, 23.7, 21.0, 16.7, 14.3, 10.0
ppm; IR (neat) 3400, 1713, 1628 cm-1; HRMS (MALDI) calcd
for C36H54O10Na (MNa+) 669.3609, found 669.3594.
C
26H34O10Na (MNa+) 529.2044, found 529.2026.
P h or bol 12-Aceta te-13-ter ep h th la te (19). White powder,
mp 189-190 °C; [R]D +17.5° (c 0.1, CH2Cl2); 1H NMR (400
MHz, acetone-d6) δ 8.18-8.08 (m, 4H), 7.56 (s, 1H), 5.68 (d, J
) 4.4 Hz, 1H), 5.57 (d, J ) 10.3 Hz, 1H), 5.33 (br s, 1H), 3.96
(AB, J ) 13.0 Hz, 2H), 3.36 (t, J ) 5.0 Hz, 1H), 3.22 (t, J )
2.2 Hz, 1H), 2.57 (d, J ) 19.4 Hz, 1H), 2.51 (d, J ) 19.4 Hz,
1H), 2.32 (dq, J ) 10.3, 6.6 Hz, 1H), 2.14 (s, 1H), 2.08 (s, 3H),
1.71 (d, J ) 1.5 Hz, 3H), 1.40 (d, J ) 5.1 Hz, 1H), 1.37 (s, 3H),
1.35 (s, 3H), 1.19 (s, 1H), 0.93 (d, J ) 6.6 Hz, 3H) ppm; 13C
NMR (100 MHz, acetone-d6) δ 208.8, 171.8, 169.0, 160.0, 143.4,
134.1, 131.2 (br), 129.0, 79.5, 78.4, 75.2, 68.5, 68.3, 57.8, 44.9,
40.7, 39.2, 37.7, 28.1, 25.0, 21.8, 18.2, 15.7, 11.2 ppm; IR (neat)
3412, 1729, 1703, 1628 cm-1; HRMS (MALDI) calcd for
P h or bol 12-[(Z)-4-Octen ed ioa te]-13-a ceta te (14). Yellow
1
oil; [R]D +10.2° (c 0.5, MeOH); H NMR (400 MHz, CDCl3) δ
7.59 (s, 1H), 5.67 (d, J ) 5.1 Hz, 1H), 5.45-5.38 (m, 3H), 4.00
(AB, J ) 13.0 Hz, 2H), 3.31-3.22 (m, 2H), 2.56 (d, J ) 19.0
Hz, 1H), 2.48 (d, J ) 19.0 Hz, 1H), 2.38 (br s, 8H), 2.16 (dq, J
) 10.3, 6.6 Hz, 1H), 2.09 (s, 3H), 1.75 (d, J ) 1.8 Hz, 3H), 1.24
(s, 3H), 1.20 (s, 3H), 1.08 (d, J ) 5.1 Hz, 1H), 0.87 (d, J ) 6.2
Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ 209.3, 177.6, 173.6,
172.8, 161.0, 140.4, 132.8, 129.0, 128.9, 128.8, 78.4, 76.9, 73.7,
68.0, 65.6, 56.0, 42.9, 38.9, 38.3, 36.3, 34.5, 34.0, 25.9, 23.9,
23.0, 22.7, 21.2, 16.9, 14.6, 10.3 ppm; IR (thin film) 3407, 1713,
1628 cm-1; HRMS (MALDI-FTMS) calcd for C30H40O10Na
(MNa+) 583.2514, found 583.2538.
C
30H34O10Na (MNa+) 577.2044, found 577.2070.
P h or bol 12-Myr ista te-13-su ccin a te (20). Colorless oil;
[R]D +6.2° (c 0.1, CH2Cl2); 1H NMR (400 MHz, CDCl3) δ 7.63-
7.60 (m, 1H), 5.67 (d, J ) 4.4 Hz, 1H), 5.61 (br s, 1H), 5.40 (d,
J ) 10.3 Hz, 1H), 4.01 (AB, J ) 12.8 Hz, 2H), 3.30-3.24 (m,
2H), 2.58 (d, J ) 19.0 Hz, 1H), 2.48 (d, J ) 19.0 Hz, 1H), 2.36-
2.31 (m, 4H), 2.172 (s, 1H), 2.167 (dq, J ) 10.3, 6.6 Hz, 1H),
2.09 (s, 3H), 1.77-1.76 (m, 3H), 1.67-1.57 (m, 4H), 1.35-1.22
(m, 19H), 1.21 (s, 3H), 1.08 (d, J ) 5.1 Hz, 1H), 0.89 (d, J )
6.6 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ 210.0, 173.93,
173.85, 161.5, 140.6, 133.0, 129.3, 78.3, 76.6, 73.7, 68.0, 65.6,
56.1, 42.8, 38.9, 38.3, 36.1, 34.6, 29.4, 29.3, 29.2, 29.13, 29.08,
29.04, 28.9, 28.8, 25.6, 25.0, 24.5, 23.7, 21.0, 16.7, 14.3, 10.0
ppm; IR (neat) 3400, 1713, 1628 cm-1; HRMS (MALDI) calcd
for C36H54O10Na (MNa+) 669.3609, found 669.3594.
P h or bol 12-Ter ep h th a la te-13-a ceta te (15). Clear liquid;
[R]D +18.1° (c 0.5, CH2Cl2); 1H NMR (400 MHz, CDCl3) δ 8.17
(d, J ) 8.3 Hz, 2H), 8.11 (d, J ) 8.3 Hz, 2H), 7.65 (s, 1H), 5.71
(d, J ) 5.4 Hz, 1H), 5.69 (d, J ) 10.3 Hz, 1H), 4.04 (AB, J )
18.8 Hz, 2H), 3.35 (t, J ) 4.9 Hz, 1H), 3.31 (t, J ) 2.4 Hz, 1H),
2.59 (d, J ) 18.8 Hz, 1H), 2.53 (d, J ) 18.8 Hz, 1H), 2.36 (dq,
J ) 10.3, 6.3 Hz, 1H), 2.13 (s, 3H), 2.11 (s, 1H), 1.78-1.76 (m,
3H), 1.38 (s, 3H), 1.20 (s, 3H), 1.16 (d, J ) 4.9 Hz, 1H), 0.94
(d, J ) 6.3 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ 210.2,
174.0, 169.6, 165.7, 161.7, 140.7, 134.4, 133.1, 130.3, 129.8,
129.2, 78.40, 78.37, 73.8, 68.0, 65.6, 56.2, 43.1, 39.0, 38.3, 36.5,
26.0, 23.7, 21.0, 17.0, 14.4, 10.0 ppm; IR (neat) 3396, 1716,
P h or bol 12-Aceta te-13-tetr a d eca n ed ioa te (21). Yellow
1
oil; [R]D +2.4° (c 0.1, CH2Cl2); H NMR (300 MHz, CDCl3) δ
J . Org. Chem, Vol. 68, No. 13, 2003 5035