Total Synthesis of Palau amine
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1 Total Synthesis of Palau amine Seiple, I. B.; Su, S.; Young, I. S.; Lewis, C. A.; Yamaguchi, J.; Baran, P. S. Angew. Chem. Int. Ed. 2009, early view Chad opkins Wipf Group Literature Presentation Chad Wipf Group Page 1 of 14 1/27/2010
2 Stylotella aurantium Palau Isolation and Biological Activity Meaning of awaiian word palau: war club Isolated in 1993 from the sea sponge Stylotella agminata collected from the Western Caroline Islands in the Republic of Palau Low acute toxicity (LD 50 13mg/kg, mice) Significant immunosuppressive and antitumor activities (IC 50 s for P-388 and A-549 were 0.1 and 0.2 µg/ml, respectively) Displays antifungal and antibacterial activities Authors note that the dust from the sponge caused allergic reactions consisting of severe shortness of breath lasting for about 4 h and skin rashes. (revised structure) Kinnel, R. B.; Gehrken,.-P.; Scheuer, P. J. J. Am. Chem. Soc. 1993, 115, Kinnel, R. B.; Gehrken,.-P.; Swali, R.; Skoropowski, G.; Scheuer, P. J. J. rg. Chad Wipf Group Chem. 1998, 63, Page of 14 1/27/2010
3 Synthetic Challenges A Formidable pponent.. Synthetic Publications: 34 PhD. Dissertations: 26 Total Synthesis: 1 (title paper) cis-5,5 trans-5,5 original structure (incorrect) Unusually high nitrogen content (/C ~ 1 : 2) ighly strained core with 8 contiguous stereocenters igh polarity translates into difficulty in performing manipulations (solubility, purifications, etc.) p stability (decomposes under basic conditions above p 6.5) Absolute stereochemistry is unknown Structure revision: Grube, A.; Kock, M. Angew. Chem. Int. Ed. 2007, 46, Buchanan, M. S.; Carroll, A. R.; Quinn, R. J. Tetrahedron Lett. 2007, 48, revised structure (correct) Kobayashi,.; Kitamura, K.; agai, K.; akao, Y.; Fusetani,.; van Soest, W. M.; Matsunaga, S. Tetrahedron Lett. 2007, 48, Chad Wipf Group Page 3 of 14 1/27/
4 ypothetical Biosynthesis 2 istidine C 2 C 2 2 C clathrodin Proline [] Mourabit, A. A.; Potier, P. Eur. J. rg. Chem. 2001, 237. Palau'amine Andrade, P.; Willoughby, R.; Pomponi, S. A.; Kerr, R. G. Tetrahedron Lett. 1999, 40, Chad Wipf Group Page 4 of 14 1/27/2010
5 roidin-derived Alkaloids Figure blatantly stolen from: Disclaimer: Relative stereochemistry unrevised Du,.; e, Y.; Sivappa, R.; Lovely, C. J. Synlett 2006, 965. Chad Wipf Group Page 5 of 14 1/27/2010
6 2 C ighlights of Selected Previous Efforts Towards Palau amine (Romo) (s)-pyroglutamic acid 2 C C TIPS Tsv Ts 1) 2, Li 4 2,6-lutidine, 170 o C 45 min,µw 2) TBDPS, Et3 DMAP, DCM 48% (2 steps) TIPS Tsv Ts TBDPS 2 Pd() 2 /C 93% TIPS Tse Ts TBDPS tartaric acid Tsv = Ts DMD, MgS 4-50 o C, DCM 99% TIPS Tse Ts TBDPS chloramine-t C 6 10, DCM -50 to rt 65-70% TIPS chlorination followed by a 1,2-migration/ring contraction Tse Ts TBDPS 1) TBAF, TF -40 o C, 79% 2) Mea, Me 65 o C, 76% correction of stereochemistry Tse Ts C 2 Me TBDPS x-ray obtained of p-bromobenzoyl derivative 1) TIPSTf, 91% 2) DIBAL-, -78 o C 3) ab 4, rt, (70%, 2 steps) TIPS Tse Ts TBDPS PPh 3, DIAD 74% TIPS Dilley, A. S.; Romo, D. rg. Lett. 2001, 3, Dransfield, P. J.; Wang, S.; Dilley, A.; Romo, D. rg. Lett. 2005, 7, Wang, S.; Dilley, A. S.; Poullenec, K. G.; Romo, D. Tetrahedron 2006, 62, Tse Ts TBDPS 2 Dransfield, Chad P. opkins J.; Wipf A. S.; Group Wang, S.; Romo, D. Tetrahedron 2006, Page 62, ; of 14 Zancanella, M. A.; Romo, D. rg. Lett. 2008, 10, 1/27/ palau'amine 2
7 Me ighlights of Selected Previous Efforts Towards Palau amine (verman) Me 2 C 2 TBS PMB TBS Me 2 C PMB Me SEM Me 2 C C 2 Me SEM TBS 13 steps from comm. material Grubbs' II (5 mol%) DCM, 40 o C 0.1M, 2 d 75-80% SEM Me 2 C TBS C 2 Me S 2 2 Et, 110 o C sealed tube 2 d, 69-71% SEM S TBS 4 steps C 2 Me SmI 2 - cleavage S-methylation -protection thiourea formation SEM Teoc MeS TBS C 2 Me S Cbz 5 steps Ac guanidine formation Teoc protecting group manipulations reduction of carbonyls acetylation MeS TBS Ac Cbz 2 3 steps eacetylation/cyclization lcohol inversion SMe Cbz 2 4 steps guanidine formation deprotection/debromination 2 2 CF 3 C CF 3 C 2-2 : 1 mixture palau'amine Katz, J. D.; verman, L. E. Tetrahedron 2004, 60, original structure (incorrect) Lanman, Chad B. opkins A.; Wipf L. Group E.; Paulini, R.; White,. S. J. Am. Page Chem. 7 of 14 Soc. 2007, 129, /27/
8 Synthesis of Functionalized Cyclopentane Core Et Et 3 steps TIPS C 2 Me Me 2 C 150 o C TIPS C 2 Me C 2 Me (x-ray) single diastereomer 1) LA 2) Ms 3) a 3 4) TBAF 64% (5 steps) 3 3 1) PMB 2) 3 85% (2 steps) PMB 3 3 1) TMSTf i-pr 2 Et then BS 2) Si 2 57% (2 steps) single diastereomer 3 3 PMB 1) Li 2) TFA 78% (2 steps) 3 3 attenuate reactivity S 2 2 2,6-lutidine 38-43% 3-3 X X B: ) ab 4 Ce 3 2) DBU 2 Boc Boc 55% (2 steps) Chlorination Side Products 3 3 ~ 15% ~ 15% Boc Boc avoids intramolecular epoxidation and/or guanidine cyclization Gosselin, P.; Bourdy, C.; Mille, S.; Perrotin, A. J. rg. Chem. 1999, 64, Yamaguchi, J.; Seiple, I. B.; Young, I. S.; Malley, D. P.; Maue, M.; Baran, P. S. Angew. Chem. Int. Ed. 2008, 47, Su, S.; Seiple, I. B.; Young, I. S.; Baran, P. S. J. Am. Chem. Soc. 2008, 130, Chad Wipf Group Page 8 of 14 1/27/2010 IBX 70% (dr 1.3 : 1) Boc Boc other oxidation conditions afforded incorrect spirodiastereomer at C14 a(c) 2 72% 3 3 Boc Boc ~ 2g prepared 19 steps, 1% overall (C) 2
9 3 3 Boc Boc (C) 2 3 Pyrrole-Acid Intermediate Boc Boc 50% aq. TFA (C) 2 3 crude Ag II 10% TFA 64% 17% rec. interm. (2 steps, 1 pot) - Addition of TFA accelerates reaction (5 min) - Completely chemoselective(!) Me 2 C brine 65% minimizes choride displacement TFAA/TFA then 2 54% Me Me 2 (pyrrole surrogate) Ac, 38 o C, 6 h then TFA, rt, 12 h C 2 t-bu 44% (overall) TM-mediated coupling conditions were unsuccessful Me Me 3 Me 3 C 2 t-bu 2 2 TFA -Me Me Me 3 3 C 2 t-bu Me C t-bu 2 C t-bu 2 C P()(Me) 2 Me 3 Me Me Me Me Kt-Bu 92% 10% Pd/C 80% t-bu 2 C Me t-bu 2 C 2 Me Me 1) DMD, acetone, 41% 2) a 3, 4, 83% 3) MeI, Ag 2 76% Me Me Seiple, Chad I. B.; opkins Su, Young, Wipf Group I. S.; Lewis, C. A.; Yamaguchi, J.; Page Baran, 9 of 14 P. S. Angew. Chem. Int. Ed. 2009, Early View. 1/27/2010
10 Completion of Racemic Palau amine 3 3 C , Pd(Ac) C EDC Bt TFA 70 o C 17% (from azide) (/-)-Palau'amine 0.6 mg as 2TFA salt The following was taken from the SI: Attempted purification of intermediates (in the above sequence) led to a reduced yield of final product due to their extreme polarity leading to difficulty in separation Purification of final product had to be performed twice on two columns (RP PLC) in 5-8 batches each Seiple, I. B.; Su, S.; Young, I. S.; Lewis, C. A.; Yamaguchi, J.; Baran, P. S. Angew. Chem. Int. Ed. 2009, Early View. what was the inspiration for the trans-annular cyclization? Chad Wipf Group Page 10 of 14 1/27/2010
11 Spectroscopic Comparison ( 1 MR) Buchanan, M. S.; Carroll, A. R.; Quinn, R. J. Tetrahedron Lett. 2007, 48, Kinnel, R. B.; Gehrken,.-P.; Scheuer, P. J. J. Am. Chem. Soc. 1993, 115, Chad Wipf Group Page 11 of 14 1/27/2010
12 Spectroscopic Comparison ( 13 C MR) Buchanan, M. S.; Carroll, A. R.; Quinn, R. J. Tetrahedron Lett. 2007, 48, Kinnel, R. B.; Gehrken,.-P.; Scheuer, P. J. J. Am. Chem. Soc. 1993, 115, Chad Wipf Group Page 12 of 14 1/27/2010
13 Inspiration for Macro-Palau amine? CF 3 C 2 - CF 3 C 2 2 TFA 70 o C CF 3 C 2 - CF 3 C 2 2 Seiple, I. B.; Su, S.; Young, I. S.; Lewis, C. A.; Yamaguchi, J.; Baran, P. S. Angew. Chem. Int. Ed. 2009, Early View o C additional unknown prdts ~ equal amounts Sharma, G. M. Drugs, Food, Sea, Myth, Reality [Intl. Symp. Proc.] 1978, 203. akadai, M.; arran, P. G. Tetrahedron Lett. 2006, 47, exemplifies the innovative retrosynthetic analysis and mechanistic thinking that underpins the Baran group s remarkable string of total synthesis - C&E, 2010, 88(2), 5. the macro-intermediate is just off the charts, and alone places Baran in rarified territory. It is not just non-obvious, it is totally counter intuitive on many levels Chad opkins Wipf Group blogpost, Jan. 2, Page of 14 1/27/2010
14 Summary First synthesis of Palau amine completed over 16 years after initial isolation Minimal protecting group operations Functionalized cyclopentane core prepared using strategic Diels-Alder, intramolecular aldol, and tandem oxidation/spirocyclization reactions Late stage chemoselective Ag(II)-picolinate oxidation installs key hemiaminal Uncatalyzed coupling of pyrrole surrogate gives access to pyrrole acid intermediate Intriguing trans-annular cyclization establishes elusive trans-5,5 ring core and completes the synthesis According to Baran, an enantioselective, scalable variant is coming soon please stay tuned. Chad Wipf Group Page 14 of 14 1/27/2010
I. B. Seiple, S. Su, I. S. Young, C. A. Lewis, J. Yamaguchi, and P. S. Baran, Angew. Chem. Int. Ed. 2009, 49,
I. B. Seiple, S. Su, I. S. Young, C. A. Lewis, J. Yamaguchi, and P. S. Baran, Angew. Chem. Int. Ed. 09, 49, 95-98. ong Ren @ The Wulff Group 03-05- 2 2 2 Synthesized naturally by Stylotella agminata Cytotoxic
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