1 Charette/Collins Synthesis Day May Université de Montréal, Montréal, Qc Charette/Collins Synthesis Day May Université de Montréal, Montréal, Qc 7th Heaven (plus Scott), and André B. Charette* Département de chimie, Université de Montréal, C.P. 6128, succ. Centre-ville, Montréal, Québec, Canada H3C 3J7 7th Heaven (plus Scott), and André B. Charette* Département de chimie, Université de Montréal, C.P. 6128, succ. Centre-ville, Montréal, Québec, Canada H3C 3J7 Total Synthesis of Daphnilongeranine C

2 Retrosynthetic Analysis Main synthons prepared from readily available starting material

3 Towards Malonate Partner J. Org. Chem. 1980, 45, 4129 J. Am. Chem. Soc. 1998, 120, 3903 Org. Lett. 2009, 11, 4358

4 Towards Malonate Partner J. Am. Chem. Soc. 2007, 129, J. Am. Chem. Soc. 1984, 106, 1079 Tetrahedron Lett. 1995, 36, Steps to First Synthon

5 Longest Linear Starts..... NOW!!!! Tetrahedron Lett. 1999, 40, 2699 Tetrahedron 1985, 41, 375 J. Am. Chem. Soc. 2007, 129, 9086 J. Org. Chem. 2003, 62, 5746 Org. Lett. 2005, 7, 5461

6 Forward and Onward! J. Org. Chem. 2003, 62, 5746 Org. Lett. 2005, 7, 5461 Tetrahedron 2005, 61, 4053 WO2009/49112 A PHILIPP, ARE YOU AWAKE???

7 Endgame Tsuji, J. Palladium Reagents and Catalysis. 2004, Wiley. Tetrahedron Lett. 1983, J. Am. Chem. Soc. 2007, 129, LONGEST LINEAR SEQUENCE !!!!!! 27 steps total 8.31 G of Product Overall yield of %

8 Thank you iNMR for nicer looking spectra