File:Podophyllotoxin Syntheses.GIF

Summary

This picture shows two syntheses of (-)-Podophyllotoxin (structure 11). one starts from the top and the other from the bottom, and the two syntheses meet in the middle. The first synthesis, J. AM. CHEM. SOC., Vol. 125, NO. 40, 2003, progresses from the top toward the center of the picture. The starting material for the first synthesis is (4S)-2-(naphtho[2,3-d][1,3]dioxol-6-yl)-4-(propan-2-yl)-4,5-dihydro-1,3-oxazole (structure 16). The second synthesis, Org. Lett., Vol. 9, No. 7, 2007, begins at the bottom of the picture and progresses toward the center. The starting material for the second synthesis is 6-Bromo-1,3-Benzodioxole-5-Carbaldehyde (structure 1).

InChI

Structure 1 InChI=1/C8H5BrO3/c9-6-2-8-7(11-4-12-8)1-5(6)3-10/h1-3H,4H2

Structure 2 InChI=1/C10H9BrO4/c11-7-4-9-8(14-5-15-9)3-6(7)10-12-1-2-13-10/h3-4,10H,1-2,5H2

Structure 3 InChI=1/C17H20O6/c1-17(2,3)23-15(18)5-4-11-8-13-14(22-10-21-13)9-12(11)16-19-6-7-20-16/h4-5,8-9,16H,6-7,10H2,1-3H3/b5-4+

Structure 4 InChI=1/C29H36O9/c1-8-9-18(27(30)38-29(2,3)4)25(17-12-23(31-5)26(33-7)24(13-17)32-6)19-14-21-22(37-16-36-21)15-20(19)28-34-10-11-35-28/h8,12-15,18,25,28H,1,9-11,16H2,2-7H3/t18-,25-/m0/s1

Structure 5 InChI=1/C27H32O8/c1-8-9-18(26(29)35-27(2,3)4)24(16-10-22(30-5)25(32-7)23(11-16)31-6)19-13-21-20(33-15-34-21)12-17(19)14-28/h8,10-14,18,24H,1,9,15H2,2-7H3/t18-,24-/m0/s1

Structure 6 InChI=1/C26H30O9/c1-26(2,3)35-25(29)17(7-8-27)23(15-9-21(30-4)24(32-6)22(10-15)31-5)18-12-20-19(33-14-34-20)11-16(18)13-28/h8-13,17,23H,7,14H2,1-6H3/t17-,23-/m0/s1

Structure 7 InChI=1/C26H32O9/c1-26(2,3)35-25(29)22-16(11-27)23(28)15-10-18-17(33-12-34-18)9-14(15)21(22)13-7-19(30-4)24(32-6)20(8-13)31-5/h7-10,16,21-23,27-28H,11-12H2,1-6H3/t16-,21+,22-,23u/m0/s1

Structure 8 InChI=1/C26H30O9/c1-26(2,3)35-25(29)22-16(11-27)23(28)15-10-18-17(33-12-34-18)9-14(15)21(22)13-7-19(30-4)24(32-6)20(8-13)31-5/h7-10,16,21-22,27H,11-12H2,1-6H3/t16-,21+,22-/m0/s1

Structure 9 InChI=1/C23H24O9/c1-27-17-5-11(6-18(28-2)22(17)29-3)19-12-7-15-16(32-10-31-15)8-13(12)21(25)14(9-24)20(19)23(26)30-4/h5-8,14,19-20,24H,9-10H2,1-4H3/t14-,19+,20-/m0/s1

Structure 10 InChI=1/C23H26O9/c1-27-17-5-11(6-18(28-2)22(17)29-3)19-12-7-15-16(32-10-31-15)8-13(12)21(25)14(9-24)20(19)23(26)30-4/h5-8,14,19-21,24-25H,9-10H2,1-4H3/t14-,19+,20-,21-/m0/s1

Structure 11 InChI=1/C22H22O8/c1-25-16-4-10(5-17(26-2)21(16)27-3)18-11-6-14-15(30-9-29-14)7-12(11)20(23)13-8-28-22(24)19(13)18/h4-7,13,18-20,23H,8-9H2,1-3H3/t13-,18+,19-,20-/m0/s1

Structure 12 InChI=1/C22H20O8/c1-25-16-4-10(5-17(26-2)21(16)27-3)18-11-6-14-15(30-9-29-14)7-12(11)20(23)13-8-28-22(24)19(13)18/h4-7,13,18-19H,8-9H2,1-3H3/t13-,18-,19+/m1/s1

Structure 13 InChI=1/C33H34O9Si/c1-7-39-32(35)33-17-40-31(34)28(33)27(19-13-25(36-2)29(38-4)26(14-19)37-3)21-15-23-24(42-18-41-23)16-22(21)30(33)43(5,6)20-11-9-8-10-12-20/h7-16,27-28,30H,1,17-18H2,2-6H3/t27-,28+,30+,33+/m1/s1

Structure 14 InChI=1/C33H34O9SSi/c1-7-38-31(34)33(19-39-32(43)42-22-16-27(35-2)29(37-4)28(17-22)36-3)14-13-21-15-25-26(41-20-40-25)18-24(21)30(33)44(5,6)23-11-9-8-10-12-23/h7-18,30H,1,19-20H2,2-6H3/t30-,33+/m0/s1

Structure 15 InChI=1/C28H31NO5Si/c1-6-31-27(30)28(26-29-22(16-32-26)18(2)3)13-12-19-14-23-24(34-17-33-23)15-21(19)25(28)35(4,5)20-10-8-7-9-11-20/h6-15,18,22,25H,1,16-17H2,2-5H3/t22-,25+,28+/m1/s1

Structure 16 InChI=1/C17H17NO3/c1-10(2)14-8-19-17(18-14)12-4-3-11-6-15-16(21-9-20-15)7-13(11)5-12/h3-7,10,14H,8-9H2,1-2H3/t14-/m1/s1

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