synthesis of leucascandrolide a via a spontaneous macrolactolization j. am. chem. soc. 2002, 124,...

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Synthesis of Leucascandrolide A via a Spontaneous Macrolactolization J. Am. Chem. Soc. 2002, 124, 13670-13671 Presented by Vijayarajan Devannah 3/19/2013 Ying Wang, Jelena Janjic, Sergey A. Kozmin

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About Leucascandrolide A Its is a highly bioactive marine macrolide isolated from new genus of calcerous sponges Leucascandra caveolata. It displays potent cytotoxicity against KB and P388 tumor cell lines ( IC ng/ml and 0.25 μg/mL respectively), and it also a strong inhibitor of animal-pathogenic yeast candida albicans. Structural Features of Leucascandrolide A It possess a 14 membered lactone It includes dioxotricyclic core It is highly unsaturated and contains oxazole in its side chain. 2

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Page 1: Synthesis of Leucascandrolide A via a Spontaneous Macrolactolization J. Am. Chem. Soc. 2002, 124, 13670-13671 Presented by Vijayarajan Devannah 3/19/2013

Synthesis of Leucascandrolide A via a Spontaneous Macrolactolization

J. Am. Chem. Soc. 2002, 124, 13670-13671

Presented by Vijayarajan Devannah3/19/2013

Ying Wang, Jelena Janjic, Sergey A. Kozmin

Page 2: Synthesis of Leucascandrolide A via a Spontaneous Macrolactolization J. Am. Chem. Soc. 2002, 124, 13670-13671 Presented by Vijayarajan Devannah 3/19/2013

About Professor Sergey A. Kozmin Education and Professional• 1991-1993 Undergraduate Research Assistant with Professor Irina P. Beletskaya Lomonosov Moscow State University, Moscow, Russia•1993-1998 Graduate Research Assistant with Professor Viresh H. RawalUniversity of• Chicago, Chicago, Illinois•1998-2000 Postdoctoral Associate with Professor Amos B. Smith, III University of Pennsylvania, Philadelphia, Pennsylvania•2000-2006 Assistant Professor, University of Chicago•2006-2011 Associate Professor, University of Chicago•2011-present Professor, University of ChicagoNotable Awards•2003 Alfred P. Sloan Fellow•2004 American Cancer Society Research Scholar•2004 Amgen Young Investigator’s Award•2004 Camille Dreyfus Teacher-Scholar Award•2005 NSF CAREER Award•2005 GlaxoSmithKline Chemistry Research Scholar 2

Page 3: Synthesis of Leucascandrolide A via a Spontaneous Macrolactolization J. Am. Chem. Soc. 2002, 124, 13670-13671 Presented by Vijayarajan Devannah 3/19/2013

About Leucascandrolide A

•Its is a highly bioactive marine macrolide isolated from new genus of calcerous sponges Leucascandra caveolata.•It displays potent cytotoxicity against KB and P388 tumor cell lines ( IC50 50 ng/ml and 0.25 μg/mL respectively), and it also a strong inhibitor of animal-pathogenic yeast candida albicans. Structural Features of Leucascandrolide A•It possess a 14 membered lactone •It includes dioxotricyclic core•It is highly unsaturated and contains oxazole in its side chain.

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Page 4: Synthesis of Leucascandrolide A via a Spontaneous Macrolactolization J. Am. Chem. Soc. 2002, 124, 13670-13671 Presented by Vijayarajan Devannah 3/19/2013

Retrosynthesis

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Page 5: Synthesis of Leucascandrolide A via a Spontaneous Macrolactolization J. Am. Chem. Soc. 2002, 124, 13670-13671 Presented by Vijayarajan Devannah 3/19/2013

Synthesis of C1-C15 Fragment

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Scheme 2

Scheme 3

Page 6: Synthesis of Leucascandrolide A via a Spontaneous Macrolactolization J. Am. Chem. Soc. 2002, 124, 13670-13671 Presented by Vijayarajan Devannah 3/19/2013

Continues……

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Scheme 4

Scheme 5

Page 7: Synthesis of Leucascandrolide A via a Spontaneous Macrolactolization J. Am. Chem. Soc. 2002, 124, 13670-13671 Presented by Vijayarajan Devannah 3/19/2013

Formation of crucial Macrocycle

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Scheme 5

Page 8: Synthesis of Leucascandrolide A via a Spontaneous Macrolactolization J. Am. Chem. Soc. 2002, 124, 13670-13671 Presented by Vijayarajan Devannah 3/19/2013

Synthesis of Oxazole side chain and completion of the target Leucascandrolide

A

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Scheme 6

Page 9: Synthesis of Leucascandrolide A via a Spontaneous Macrolactolization J. Am. Chem. Soc. 2002, 124, 13670-13671 Presented by Vijayarajan Devannah 3/19/2013

Conclusion• Racemic Leucascandrolide A was synthesized in longest linear

sequence of 18 steps from commercially available precursors. 500 MHz 1H NMR and 125 MHz 13C NMR spectra of synthetic Leucascandrolide A was in excellent agreement with those reported in literature.

• Total yield is 2%

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Page 10: Synthesis of Leucascandrolide A via a Spontaneous Macrolactolization J. Am. Chem. Soc. 2002, 124, 13670-13671 Presented by Vijayarajan Devannah 3/19/2013

Thank You

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