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Charette/Collins Synthesis DayMay 14 2010

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

andre.charette@umontreal.ca

Total Synthesis of Daphnilongeranine C

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Retrosynthetic Analysis

Main synthons prepared from readily available starting material

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Towards Malonate Partner

J. Org. Chem. 1980, 45, 4129

J. Am. Chem. Soc. 1998, 120, 3903

Org. Lett. 2009, 11, 4358

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Towards Malonate Partner

J. Am. Chem. Soc. 2007, 129, 10356J. Am. Chem. Soc. 1984, 106, 1079

Tetrahedron Lett. 1995, 36, 2531

10 Steps to First Synthon

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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, 5746Org. Lett. 2005, 7, 5461

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Forward and Onward!

J. Org. Chem. 2003, 62, 5746Org. Lett. 2005, 7, 5461

Tetrahedron 2005, 61, 4053

WO2009/49112 A1 2009

PHILIPP, ARE YOU AWAKE???

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Endgame

Tsuji, J. Palladium Reagents and Catalysis. 2004, Wiley. Tetrahedron Lett. 1983, 24 3841.

J. Am. Chem. Soc. 2007, 129, 10356

16 LONGEST LINEAR SEQUENCE !!!!!!

27 steps total

8.31 G of Product

Overall yield of 83.45286%

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Thank you iNMR for nicer looking spectra