Andrew ratz Daphniphyllum Alkaloids Evans Group Seminar, June 1993 Synthesis of Methy! Homodaphniphyllate cont'd i Proposed Biosynthesis of the Daphniphyllum Alkaloid H30 0 alene dialdehyde 1. Me2C EtO)2 POCI O2P(OEt) OHC、 OHC EtoH,120°c Tet Lett1969,2145 Pure& App/. Chem. 1989, 61, 289 J.Am.chem.Soc.1986,108,8274 2D-0312/110011:27AMAndrew Ratz Daphniphyllum Alkaloids Evans Group Seminar, June 1993 LDA, THF MeCHO 100% H30+ 2. LDA, THF, HMPA (EtO)2POCl 73% Li/EtNH2 64% 120 atm H2 Pd(OH)2 EtOH, 120°C 81% ?? 1. Jones 2. MeOH, H+ + + 68% 13% 1:1 ratio Synthesis of Methyl Homodaphniphyllate cont'd Tet. Lett. 1969, 2145. H OBn Me N O O O N O Me O O HO Me R H H R Me O EtO)2PO2 iPr O2P(OEt)2 Me O N N OBn O O Me Me N O HO H OBn OBn N N OH H iPr H H H OH N iPr N OH H iPr H H H H H iPr H CO2Me H N H Me Me R N 1. Me2CuLi (EtO)2POCl 83% Pure & Appl. Chem. 1989, 61, 289 J. Am. Chem. Soc. 1986, 108, 8274 Proposed Biosynthesis of the Daphniphyllum Alkaloids Squalene Dialdehyde pyridoxamine Me CHO OHC Me Me Me Me Me OHC R R N N OP* HO Me N Ar OHC R R R R OHC N Ar NH O R Ar NH NH R R N Me Me Me N Me R Me Me R HN Me Me 32D-03 12/11/00 11:27 AM