Petasis-Ferrier Rearrangement
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1 Petasis-Ferrier Rearrangement Name Reaction Presentation Anil Kumar Gupta Wulff Group February 13, 2009
2 Ferrier Reaction Type I Ferrier Reaction (1962) LA = BF 3.Et 2, SnCl 4,I 2 Nuc = R,S, N = -acyl, = C 2 --acyl, LG = -acyl, Ts LA R Nu Nu 2 LG 1,2-glycal LA LG allyloxycarbenium ion 2,3-unsaturated glycosyl compound Ferrier, R. J.; verend, W. G.; Ryan, M. E. J. Chem. Soc. 1962, Type II Ferrier Rearrangement (1979) Xg gx Me Me gx 2 R 5 2 R 5 R 4 R 5 2 R 5 R 4 exocyclic enol ether, R 4, R 5 = -acyl, -alkyl R 4 R 4 ketoaldehyde!-hydroxy cyclohexanone Ferrier, R. J. J. Chem. Soc., Perkin Trans ,
3 Dr. Robin J. Ferrier PhD, University of Edinburgh, UK, 1957, Synthetic and mechanistic studies of monosaccharide compounds Professor, London University, UK Post-doctoral, Berkeley, Professor Melvin Calvin Chair of rganic Chemistry, Victoria University of Wellington, New Zealand,1970 Consultant, GlycoSyn, Industrial Research Limited (IRL), New Zealand
4 Petasis Rearangement Petasis Rearrangement (1996) cyclic enol acetal LA LA Ferrier Rearrangement Type II (1979) LA LA = [Al(i-Bu) 3 ] MPV Petasis, N. A.; Lu, S.-P. Tetrahedron Lett. 1996, 37, tetrahydropyran Xg gx Me Me gx 2 exocyclic enol ether 2 2!-hydroxy cyclohexanone Ferrier, R. J. J. Chem. Soc., Perkin Trans ,
5 Dr. Nicos A. Petasis B.S. Chemistry, Aristotle University of Thessaloniki, Greece, 1978 Ph.D. rganic Chemistry, University of Pennsylvania, 1983 Research Associate and Adjunct Lecturer, University of Pennsylvania, arold and Lillian Moulton Chair and Professor in Chemistry, present University of Southern California New Synthetic Methods and Strategies, organotitanium, organoboron, combinatorial chemistry and catalysis
6 Petasis-Ferrier Rearrangement : Tetrahydrofuran BF 3 Et 2 Et 2!-hydroxy 1,3-dioxolaneacid 4-one = Ph, = = Ph, = 90 % yield >99 % syn Cp 2 TiMe 2 TF 65 C 2 C = Ph, = in the product enol acetal i-bu 3 Al C 2 PhMe R 0 or 65 C 2 substituted tetrahydrofuran 10 examples 50-91% yield 2 C Me Ph c Me Al i Bu 3 Ph a b i Bu 3 Al Me a c b Ph 5-(enolendo)- endo-trig i Bu 3 Al Me a c b Ph 2 C Me Ph c Me * Chiral Starting Material i Bu 3 Al a b i Bu 3 Al Me Ph a Isomerize c b Ph i Bu 3 Al Me Petasis, N. A.; Lu, S-P. J. Am. Chem. Soc. 1995, 117, a c b Ph
7 Substrate Scope =, 65 C a Prepared according to literature procedures. Compound 3h was prepared via the TMSTfcatalyzed reaction between tbuc and the bis-tms derivative of glycolic acid.'" while compounds 3e.d were prepared from the aldehyde and glycolic acid in the presence of BF 3 Et 2 b Yields were determined following isolation by distillaition or chromatography and were not optimized. c Prepared by the reaction of 3 with dimethyltitanocenc at 65 C in TF, d All reactions were carried out with 2 equiv of the aluminum reagent in toluene at the indicated temperature. Petasis, N. A.; Lu, S-P. J. Am. Chem. Soc. 1995, 117,
8 Substrate Scope = Me, 0 C or Ph, -78 C Dec. = Decomposed Petasis, N. A.; Lu, S-P. J. Am. Chem. Soc. 1995, 117,
9 Petasis-Ferrier Rearrangement : Tetrahydropyran!-hydroxy acid TMSCl TEA TMS PPTs,Ph," R 4 TMS TMSTf DCM - 20 C C 2 R 4 1,3-dioxane-4-one enol acetal Cp 2 TiMe 2 TF 65 C R 4 i-bu 3 Al PhMe -78 C R 4 substituted tetrahydropyran X C 2 PCC DCM Y C 2 R 4 A: X=, Y= B: Y=, X= * Chiral Starting Material Major product depends upon substitution pattern Petasis, N. A.; Lu, S.-P. Tetrahedron Lett. 1996, 37,
10 Petasis-Ferrier Rearrangement : Tetrahydropyran Mechanism: Me C 2 3 Al i Bu 3 enol acetal Me R 4 Al i Bu 2 C R 4 i Bu 3 Al C 2 R 4 Major when = C 2 R 4 [3,3] oxocarbenium enolate intramolecular reduction i Bu 3 Al C 2 Al i Bu 3 R 4 6-(enolendo)- endo-trig C 2 R 4 Petasis, N. A.; Lu, S.-P. Tetrahedron Lett. 1996, 37,
11 Substrate Scope B:A Petasis, N. A.; Lu, S.-P. Tetrahedron Lett. 1996, 37,
12 Petasis-Ferrier Rearrangement : Main Features The straightforward construction of the substrate enol acetals allows the stereocontrolled assembly of complex fragments. The configuration of the acetal carbon is retained or enhanced during the rearrangement. The rearrangement of 5-membered enol acetals takes place at a much higher temperature than for 6-membered substrates.(may be due more facile 6-(enolendo)-endo-trig cyclization) Trialkylaluminum were found to be the most effective reagents ( i- Bu 3 Al, Me 3 Al and Me 2 AlCl) The stereoselective reduction (last step) depends on the substitution pattern and occur when i-bu 3 Al used ( not occurs if Me 2 AlCl used) Drawback: lefination step can lead to olefin stereoisomers when applied titanocene is other than Dimethyl titanocene.
13 Nitrogen Analogue to Petasis-Ferrier Rearrangement N 2 = Me, Ph, Bn!-amino ester Me Cl TEA, DCM Na 2 S 4 N Cp 2 TiMe 2 Me (1.8 equiv.) = Ar, Alk = Me, PhMe-TF MW 65 C 3-10 min N C 2 Me N C 2 substituted Piperidinones N C 2 Me N Me C 2 N Me C 2 Me Me N C 2 1., 2 2. basify N C 2 N C 2 Adriaenssens, L. V.; artley, R. C. J. rg. Chem. 2007, 72,
14 Substrate Scope Adriaenssens, L. V.; artley, R. C. J. rg. Chem. 2007, 72,
15 Variant of Petasis-Ferrier Rearrangement Kulinkovich Reaction 70% Ti(-iPr) 4 (0.1 equiv) EtMgBr (3 equiv) TF/Et 2 (4:1) xepanes Neil, E.; Kingree, S. V.; Minbiole, K. P. C. rg. Lett. 2005, 7,
16 Substrate Scope Neil, E.; Kingree, S. V.; Minbiole, K. P. C. rg. Lett. 2005, 7,
17 Mechanism Benzylic cation Neil, E.; Kingree, S. V.; Minbiole, K. P. C. rg. Lett. 2005, 7,
18 Application to Total Synthesis (+)-Phorboxazole A Smith, A. B., III; Verhoest, P. R.; Minbiole, Kevin P.; Lim, J. J. rg Lett 1999, 1, (b) Smith, A. B., III; Minbiole, K. P.; Verhoest, P. R.; Beauchamp, T. J. rg Lett 1999, 1, (c) Smith, A. B., III; Verhoest, P. R.; Minbiole, K. P.; Schelhaas, M. J. Am. Chem. Soc. 2001, 123, (d)smith, A. B., III; Minbiole, K. P.; Verhoest, P. R.; Schelhaas, M. J. Am. Chem. Soc. 2001, 123, (e) Smith, A. B., III; Razler, T. M.; Ciavarri, J. P.; irose, T.; Ishikawa, T. rg. Lett. 2005, 7, (f) Smith, A. B.; Razler, T. M.; Ciavarri, J. P.; irose, T.; Ishikawa, T.; Meis, R. J. rg. Chem. 2008, 73, (g) Smith, A. B., III; Razler, T. M.; Meis, R.; Pettit, G. R. J. rg. Chem. 2008, 73, (+)-Zampanolide and (+)-Dactylolide (a) Smith, A. B., III; Safonov, I. G.; Corbett, R. M. J. Am. Chem. Soc. 2001, 123, (b) Smith, A. B., III; Safonov, I. G. rg. Lett. 2002, 4, (c) Smith, A. B., III; Safonov, I. G.; Corbett, R. M. J. Am. Chem. Soc. 2002, 124,
19 Application to Total Synthesis (+)-Spongistatin 1 (a) Smith, A. B., III; Zhu, W.; Shirakami, S.; Sfouggatakis, C.; Doughty, V. A.; Bennett, C. S.; Sakamoto, Y. rg. Lett. 2003, 5, (b) Smith, A. B., III; Sfouggatakis, C.; Gotchev, D. B.; Shirakami, S.; Bauer, D.; Zhu, W.; Doughty, V. A. rg. Lett 2004, 6, (-)-Kendomycin (a) Smith, A. B., III; Mesaros, E. F.; Meyer, E. A. J. Am. Chem. Soc. 2005, 127, (b) Smith, A. B., III; Mesaros, E. F.; Meyer, E. A. J. Am. Chem. Soc. 2006, 128,
20 Application to Total Synthesis (-)-Clavosolide A Smith, A. B., III; Simov, V. rg. Lett. 2006, 8, (-)-kilactomycin (a) Smith, A. B., III; Basu, K.; Bosanac, T. J. Am. Chem. Soc. 2007, 129, (b) Smith, A. B., III; Bosanac, T.; Basu, K. J. Am. Chem. Soc. 2009, 131, *Smith, A. B., III; Fox, R. J.; Razler, T. M. Acc. Chem. Res. 2008, 41,
21 Dr. Amos B. Smith Bucknell University's first combined four-year B.S.- M.S. degree in Chemistry, 1966 PhD,1972 & Research Associate at Rockefeller University. Professor, Department of Chemistry at the University of Pennsylvania, 1973 Currently, Rhodes-Thompson Professor of Chemistry, a Member of the Monell Chemical Senses Center, the Associate Director of the Penn Center for Molecular Discovery (PCMD), First Editor-in-Chief of the new American Chemical Society journal, rganic Letters, 1998
22 Phorboxazole A Smith, A. B., III; Minbiole, K. P.; Verhoest, P. R.; Schelhaas, M. J. Am. Chem. Soc. 2001, 123,
23 Retrosynthetic Analysis Smith, A. B., III; Minbiole, K. P.; Verhoest, P. R.; Schelhaas, M. J. Am. Chem. Soc. 2001, 123,
24 Initial Attempts towards P-F Reaction Smith, A. B., III; Minbiole, K. P.; Verhoest, P. R.; Schelhaas, M. J. Am. Chem. Soc. 2001, 123,
25 ptimization of P-F Reaction But failed Smith, A. B., III; Minbiole, K. P.; Verhoest, P. R.; Schelhaas, M. J. Am. Chem. Soc. 2001, 123,
26 Inherent Pseudo symmetry of P-F Reaction Unproductive Al coordination Yield = 89 % Productive Al coordination
27 P-F Reaction for other fragment Smith, A. B., III; Minbiole, K. P.; Verhoest, P. R.; Schelhaas, M. J. Am. Chem. Soc. 2001, 123,
28 Mechanistic Rationale Smith, A. B., III; Minbiole, K. P.; Verhoest, P. R.; Schelhaas, M. J. Am. Chem. Soc. 2001, 123,
29 Thanks
30 Application to Total Synthesis (+)-Phorboxazole A [4] (a) Smith, A. B., III; Verhoest, P. R.; Minbiole, Kevin P.; Lim, J. J. rg Lett 1999, 1, (b) Smith, A. B., III; Minbiole, K. P.; Verhoest, P. R.; Beauchamp, T. J. rg Lett 1999, 1, (c) Smith, A. B., III; Verhoest, P. R.; Minbiole, K. P.; Schelhaas, M. J. Am. Chem. Soc. 2001, 123, (d)Smith, A. B., III; Minbiole, K. P.; Verhoest, P. R.; Schelhaas, M. J. Am. Chem. Soc. 2001, 123, (+)-Zampanolide and (+)-Dactylolide [3] (a) Smith, A. B., III; Safonov, I. G.; Corbett, R. M. J. Am. Chem. Soc. 2001, 123, (b) Smith, A. B., III; Safonov, I. G. rg. Lett. 2002, 4, (c) Smith, A. B., III; Safonov, I. G.; Corbett, R. M. J. Am. Chem. Soc. 2002, 124, (+)-Spongistatin 1 [2] (a) Smith, A. B., III; Zhu, W.; Shirakami, S.; Sfouggatakis, C.; Doughty, V. A.; Bennett, C. S.; Sakamoto, Y. rg. Lett. 2003, 5, (b) Smith, A. B., III; Sfouggatakis, C.; Gotchev, D. B.; Shirakami, S.; Bauer, D.; Zhu, W.; Doughty, V. A. rg. Lett 2004, 6, (-)-Kendomycin [2] (a) Smith, A. B., III; Mesaros, E. F.; Meyer, E. A. J. Am. Chem. Soc. 2005, 127, (b) Smith, A. B., III; Mesaros, E. F.; Meyer, E. A. J. Am. Chem. Soc. 2006, 128, (-)-Clavosolide A [1] Smith, A. B., III; Simov, V. rg. Lett. 2006, 8, (-)-kilactomycin [2] (a) Smith, A. B., III; Basu, K.; Bosanac, T. J. Am. Chem. Soc. 2007, 129, (b) Smith, A. B., III; Bosanac, T.; Basu, K. J. Am. Chem. Soc. 2009, 131, *Smith, A. B., III; Fox, R. J.; Razler, T. M. Acc. Chem. Res. 2008, 41,
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