Silenes in organic synthesis: a concise synthesis of (±)-epi-picropodophyllin
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1 lenes in organic synthesis: a concise synthesis of (±)-epi-picropodophyllin obert D. C. Pullin, Jonathan D. Sellars, and Patrick G. Steel* rg. Biomol. Chem., 2007, 5, H H C Adam Hoye Current Literature ct. 27th, 2007 Adam Wipf Group 1 10/29/2007
2 Classic organosilicon chemistry H + tbu 2 Cl imidazole, DMF 2 tbu 3 Li 3 CH 3 E + 3 Et X - (- 3 X) E 3 E + 3 E X - (- 3 X) E 3 E + 3 E X - (- 3 X) E n 2 X 2 H 2 H H -H 2 n Adam Wipf Group 2 10/29/2007
3 ecent advances in organosilicon chemistry -Denmark (J. Am. Chem. Soc., 2007, 129, 2774) Bn Bn TES Li 2 HCl 89% [ucl 2 (p-cymene)] 2 H 2 = H TES = H, 84% I Piv Pd 2 (dba) 3 CHCl 3 82% Bn TES Piv Bn H H H H H H Papulacandin D -Woerpel (J. Am. Chem. Soc., 2005, 127, 2046) 1 2 AgCCF 3 (1-5 mol%) % (93:7 d.r.) Adam Wipf Group 3 10/29/2007
4 lenes: a brief history -In 1912 Schlenk and enning reported silene synthesis by dehydration of a silanol (release of H 2 ) -Kipping showed product was actually a siloxane and concluded multiple bonds to were not a realistic objective Gusel nikov and Flowers: 450 C -CH 2 =CH 2 H H H 2 3 H Brook (photolysis of acylsilanes)- steric bulk on the carbon atom key to moderating silene reactivity (stability) 3 ( 3 ) 3 hv 3 3 unchanged after several years although if exposed to air disappears in a puff of smoke ttosson, H.; Steel, P. G. Chem. Eur. J. 2006, 12, Brook et al. J. Am. Chem. Soc. 1982, 104, Adam Wipf Group 4 10/29/2007
5 lenes: a brief history -Steric stabilization of silenes Electronic stabilization of silenes: reversed =C bond polarity (that is δ- =C δ+ instead of δ+ =C δ- ) leads to lower release of energy upon dimerization; slower rates of addition to silicon dative stabilization silenolates 3 N N Extension into allenyl and aryl systems: CH( 3 ) 2 ( 3 ) 2 HC CH( 3 ) 2 ttosson, H.; Steel, P. G. Chem. Eur. J. 2006, 12, Adam Wipf Group 5 10/29/2007
6 lenes: preparation and general reactivity Common methods of preparation: General silene reactivity: hv 3 TMS 3 Nu-H Nu! X C' 2 ' ' X 2 ( 3 ) 3 Li 3-3 Li 3 Cl Li - LiCl K 3 3 K 3 3 K -40 C H ( 3 ) 2 (94%) ttosson, H.; Steel, P. G. Chem. Eur. J. 2006, 12, TMS 2 C 180 C C 2 TMS C 2 ( 3 ) 2 C 2 Adam Wipf Group 6 10/29/2007
7 Tetralin lignan lactones Podophyllotoxin 1 = H, 2 = H Isopodophyllotoxin 1 = H, 2 = H Epipodophyllotoxin 1 = H, 2 = H Epiisopodophyllotoxin 1 = H, 2 = H Podophyllotoxin is a potent antimitotic agent, but highly toxic. H H S H H Picropodophyllotoxin Epipicropodophyllotoxin 1 = H, 2 = H 1 = H, 2 = H N 2 H H HN H H H Etoposide Tenoposide DNA topoisomerase II inhibitors (used clinically, but poor solubility and growing drug resistance) Sellars, J. D.; Steel, P. G., Eur. J. rg. Chem., 2007, 3815 GL-331 In phase II trials (more potent, less resisted) Adam Wipf Group 7 10/29/2007
8 Lignan syntheses Typical strategies to construct the core: MsCl, Et 3 N 56% C 2 H C 2 H H Ar Ar 1 2 A B C D H! H 2 C C 2 H C 2 Ar Ar 90% Ar C 2 S S S S LDA 79% Ar Ar H Vanderwalle et al., Tetrahedron, 1991, 47, 4675 Charlton, J. L., Koh, K., J. rg. Chem., 1992, 57, 1514 Harrowven, D. C., Tetrahedron, 1993, 49, 9039 Florio et al., rg. Lett., 2005, 7, 4895 H Li W(C) pyridine N-oxide 52-83% H Adam Wipf Group 8 10/29/2007
9 Previous work in the Steel group ( 3 ) 3 1. KtBu or Li, THF, rt, 2 or 18 h 2. MgBr 2, Et 2 3 MgBr 3 CH H Et 2, -78 C 3 3 = (52%), C 3 H 7 (74%), (49%), i-bu (58%), t- Bu (37%), c-c 6 H 11 (38%), (68%) H ( 3 ) 2 BuLi/Li LiBr 3 H Li LiBr -TMSLi Li TMS Li Br ( 3 ) 2 3 TMS 3 Sanganee, M. J.; Steel, P. G.; Whelligan, D. K., rg. Biomol. Chem., 2004, 2, 2393 Adam Wipf Group 9 10/29/2007
10 Previous work in the Steel group 1 H 3 3 Diene n-buli, Et 2, rt, then -78 C, LiBr, warming to -30 C 22 h i Pr i Pr i Pr i Pr 50% (83:9:8) 42% (83:17) 28% (89:7:4) 45% (74:20:6) 38% (86:9:4:1) 28% (80:14:4:2) 3 BF 3 2AcH, F 3 H 2 2, KF, H CHCl 3 KHC 3, THF/H 74% H 2, Pd/C 3 BF 3 2AcH, CHCl 3 3 F H 2 2, KF, KHC 3, THF/H 43% (2 steps) H TPAP, NM H 76% 85% (2 steps) (92:8 d.r.) Berry, M. B.; Griffiths,. J.; Sanganee, M. J.; Steel, P. G.; Whelligan, D. K., rg. Biomol. Chem.2004, 4, 2381 Berry, M. B.; Griffiths,. J.; Sanganee, M. J.; Steel, P. G.; Whelligan, D. K., Tetrahedron Lett., 2003, 44, 9135 Sanganee, M. J.; Steel, P. G.; Whelligan, D. K., rg. Biomol. Chem., 2004, 2, 2393 Adam Wipf Group 10 10/29/2007
11 Sakurai reactions with cyclic allyl silanes With electron-rich aromatics: 3 CH() 2, BF 3 Et 2, DCM, 0 C 60% F 3 3 F 3 BF 3 i. 4-()C 6 H 4 CH() 2, BF 3 ˇEt 2 ii. H 2 2, KHC 3 2 X 27% (5:1 d.r.) H 2 X H 2 2, KHC 3, THF/H 80% product oxidation 2 X H H Sellars, J. D.; Steel, P. G.; Turner, M., Chem. Commun., 2006, 2385 Steel et al. rg. Biomol. Chem., 2007, 5, 2841 Adam Wipf Group 11 10/29/2007
12 Current paper ( 3 ) 3 i. KtBu, THF ii. MgBr 2 Et 2 iii. CH, Et 2 40% i. n-buli, KtBu ii. B() 3, -78 C iii. H 2 2, NaH iv. TBSCl, Imidazole 43% H 3 3 TBS nbuli, LiBr, THF, -20 C 60% = TBS = Ac 3 i. ptsh ii. AcCl (45 %) Ac 3 i. BF 3 Et 2, DCM, 0 C ii. H 2 2, KHC 3, THF/H H H H 53% (20 : 1 d.r.) s 4 (cat.), NaI 4 2,6-lutidine, THF/H 2 58% H H 3:1 mixture of anomers H formed if unprotected alcohol used Adam Wipf Group 12 10/29/2007
13 Current paper H H NIS, Bu 4 NI (0.4 eq.), DCM H 63% epi-picropodophyllin HCl, THF KHMDS H H Adam Wipf Group 13 10/29/2007
14 Conclusions -Access to tetralin lignan lactone family using silene cycloaddition/cyclic allylsilane Sakurai reactions -Highly modular synthesis; facilitates future analogue development -Truly concise synthesis (9 steps, 2.2% overall yield) H H H 3 3 Adam Wipf Group 14 10/29/2007
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