1. Asymmetric Total Synthesis of Caribenol A Author: Zhen Yang J. Am. Chem. Soc. 2010, 132, 13608 Presented by Daniel Roberts April 6 th 2014

2. Zhen Yang Degrees 1978-82 B.S. Pharmaceutical Chemistry, Shenyang College of Pharmacy 1983-86 M.S. Pharmaceutical Chemistry, Shenyang College of Pharmacy 1989-92 Ph.D. Chemistry, Chinese University of Hong Kong Academic Career 1992-95 Postdoctoral Fellow, Dept. of Chemistry, Scripps Research Inst. 1995-98 Assistant Professor, Dept of Chemistry, Scripps 2001-05 Institute Fellow, Dept. Cell Biology, Harvard Medical School 2002- Present, Changjiang Professor of Chemistry, Peking University Honors 2000 The National Science Fund for Distinguished Young Investigator Award (abroad), NSF of China (and 2004) 2005 Eli Lilly Scientific Excellence Award (China) 2009 Baogang Distinguished Teaching Award of Peking University 2010 Wuxi Pharma Life Science Excellence Award (Golden Metal) 1

3. Caribenol A First isolated in 2007 from West Indian gorgonian octocoral Shows strong inhibitory activity against mycobacterium tuberculosis (H 37 Rv), which causes tuberculosis. Caribenol A has an unprecedented tricarbocyclic ring system in that all three methyl groups are cis and contains a 5 hydroxyfurnan motif Chemically scarce 2

4. RetroSynthesis 3 Carbenol A

5. Forward Synthesis 4 t-BuLi, Et 2 O -78 c PCC, CH 2 Cl 2 LiBEt 3 H,THF TBSOTf, Et 3 N

6. Forward Synthesis 5 Dibal, DCM -78 c DMP, NaHCO 3 rt n-BuLI, THF -78 c DMP, NaHCO 3 rt

7. Forward Synthesis 6 Diels - Alder BHT 120 c Rh(PPh 3 ) 3 Cl, H 2 HF/Py, THF

8. Forward Synthesis 7 NaBH 4 CeCl 3 7H 2 O EtOH 0c0c TPAP, NMO, 4 A MS, DCM Pd/C, H 2,THF KHMDS, THF Comins Reagent -78 c

9. Forward Synthesis 8 Pd(PPh 3 ) 4, Me 2 Zn, THF rt O 2, DMF, K 2 CO 3 P(OEt) 3 60 c, 80 hr

10. 9 Finished