Total Synthesis and Stereochemical Reassignment of () -Indoxamycin B - PowerPoint PPT Presentation

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Total Synthesis and Stereochemical Reassignment of () -Indoxamycin B Jeker, O. F.; Carreira, E. M. Angew. Chem. Int. Ed. 2012 , 51 , 3474 3477 Current Literature Jie Xu 06.09.12 Jie Xu @ Wipf Group Page 1 of 11 11/15/2012 Isolation

Total Synthesis and Stereochemical Reassignment of (±) -Indoxamycin B Jeker, O. F.; Carreira, E. M. Angew. Chem. Int. Ed. 2012 , 51 , 3474 – 3477 Current Literature Jie Xu 06.09.12 Jie Xu @ Wipf Group Page 1 of 11 11/15/2012
Isolation � Isolated from saline cultures of marine-derived actinomycetes � Structure assigned by MS and NMR ( 1 H, 13 C, HMBC, NOSEY ) and chemical methods (Mosher Ester Analysis) Indoxamycins A and F have been shown to display growth inhibition against � HT-29 tumor cell lines ( IC 50 = 0.59 µm and 0.31 µm, respectively ) . Sato, S.; Iwata, F.; Mukai, T.; Yamada, S.; Takeo, J.; Abe, A.; Kawahara, H. J. Org. Chem. 2009 , 74 , 5502 – 5509. Sato, S.; Iwata, F.; Yamada, S.; Takeo, J.; Abe, A.; Kawahara, H. (Nippon Suisan Kaisha, Ltd.), WO 113725, 2010 . Jie Xu @ Wipf Group Page 2 of 11 11/15/2012
Structure � 5,5,6-Tricyclic carbon skeleton with six contiguous asymmetric centers � Three quaternary stereo centers � Tri-substituted alkene side chain � α , β -unsaturated carboxylic acid side chain Indoxamycin B Jie Xu @ Wipf Group Page 3 of 11 11/15/2012
Retrosynthetic Analysis � Saucy-Marbet Rearrangement (Propargyl Claisen) Allene Hydroalkoxylation � � Oxidative Carboannulation Jie Xu @ Wipf Group Page 4 of 11 11/15/2012
Saucy-Marbet Rearrangement propargyl vinyl ether -> β -keto allene Gold catalyzed reaction Stereo-specific Saucy, G.; Marbet, R. Helv. Chim. Acta. 1967 , 50 , 1158 – 1167. Sherry, B. D.; Toste, F. D. J. Am. Chem. Soc. 2004 , 126 , 15978 – 15979. Jie Xu @ Wipf Group Page 5 of 11 11/15/2012
Synthesis � Reluctant to undergo conjugate addition –> anionic oxy-Cope Indoxamycin B Saguesa type oxidative carboannulation � Jie Xu @ Wipf Group Page 6 of 11 11/15/2012
Au(I) Catalyzed Reaction A: 4,4’-thiobis(2- B: chloro[2-(di-tert- � � tert-butyl-5- butylphosphino) methylphenol) biphenyl]gold(I) Indoxamycin B Jie Xu @ Wipf Group Page 7 of 11 11/15/2012
Side Chain Installation Indoxamycin B Jie Xu @ Wipf Group Page 8 of 11 11/15/2012
Spectrum Conflict � Neither isomers match the natural product � Inconstant on 1 H 13 C Jie Xu @ Wipf Group Page 9 of 11 11/15/2012
Structure Reassignment Pottasium Salt � Indoxamycin B data matches Jie Xu @ Wipf Group Page 10 of 11 11/15/2012
Summary � The first synthesis of (±) -Indoxamycin B and their family members (24 steps 1% overall yield) � Sigma tropic rearrangement � Various metal used (Li, Pd, Ti, V, Au, Sm, Mn) � Structure reassignment Jie Xu @ Wipf Group Page 11 of 11 11/15/2012

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