Asymmetric Synthesis of Medium-Sized Rings by Intramolecular Au(I)-Catalyzed Cyclopropanation
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1 Asymmetric Synthesis of Medium-Sized ings by Intramolecular Au(I)-Catalyzed Cyclopropanation 1 2 Iain D. G. Watson, Stefanie itter, and F. Dean Toste JACS, ASAP, 1/22/2009 DI: /ja mol% ()-xylylbinap(aucl) 2, 5 mol% AgSbF 6 C 3 N 2, -25 C n= 0 to 3 up to 92% ee 1 2 Christopher osenker Wipf Group - Current Literature February 14, 2009 Chris Wipf Group Page 1 of 14 2/15/2009
2 Medium-sized rings Ac Spartidienedione Bz Ac = PhCN(Ph)C()C Taxol Vulgarolide Ac Acetoxycrenulide C Variecolin Epoxydictymene Synthetically obtained generally through various cycloaddition combinations; LA, radical, transition metal catalyzed cyclizations; and oxidative/reductive processes. Cyclization strategies for medium sized rings are difficult due to entropic factors and transannular interactions. Mehta, G. & Singh, V. Chem. ev. 1999, 99, 881 Yet, L. Chem. ev. 2000, 100, Chris Wipf Group Page 2 of 14 2/15/2009
3 Enantioselective synthesis of medium-sized rings Cobalt catalyzed [ ] cycloaddition [5 + 2] Cycloaddition of vinylcyclopropanes and π-systems Co(acac) 2, Et 2 AlCl (4 eq) ()-PPS, C 6 6 = Me, Et, (C 2 )TMS, (C 2 ) 3 (Ac/TBS) X [h(()-binap)] + SbF 6 - X =, NTs, malonate =, Me, C 2 Bn X 72% to 95% yield 22% to >99% ee 40% to 66% yield Lautens, M. J. rg. Chem. 1993, 58, % to 79% ee Wender, P. A. J. Am. Chem. Soc. 2006, 128, Mo-catalyzed asymmetric olefin metathesis MM MM 5 mol% Mo(L*) C 6 6, TF (1 eq), 18 h 75% ee; >98% conv oveyda, A.. & Schrock,.. Proc. Nat. Acad. Sci. U.S.A. 2004, 101, 5805 h-catalyzed carbonyl hydroacylation to lactones 5% Ln*[h] = aryl/alkyl Dong, V. M. J. Am. Chem. Soc. 2008, 130, % to 99% yield 99% ee Chris Wipf Group Page 3 of 14 2/15/2009
4 Enantioselective synthesis of medium-sized rings Cu(I) catalyzed cyclopropanation to form macrocycles Me CN 2 1% Cu(bis-ox)PF 6 10, 15, 20 membered rings 90% to 42% yield (poor dr for large rings) 80% to 90% ee Doyle, M. P. J. Am. Chem. Soc. 2000, 122, Me Asymmetric tandem cyclopropanation/cope rearrangement h N S 2 h 4 N 2-78 C, 93% ee =4-(C )C 6 4 then heat 140 C 70% Davies,. M. L. Tet. Let , 37, Chris Wipf Group Page 4 of 14 2/15/2009
5 Intramolecular enyne cycloisomerizations ydroarylation of alkynes N 1 N 1 Au I Au III N 2 = N N Echavarren, A. M. Angew. Chem., Int. Ed , N 1 2 Ac Intramolecular cyclopropanation PtCl 2, AuCl 3, or Au I Ac ( ) m ( ) m n = 1, 2, 3 m = 1, 2, 3 Fensterbank, L. & Malacria, M. Adv. Synth. Catal , 43. 1,3-addition of alkenylcarbenoid intermediate lefin cyclopropanation to synthesize allocolchicinoid Ac 5% Pt II, (Au I ) + 50 C, 10 h 1,3 acyl transfer allene intermediate Ac Me Me Me Ac 1) 1% (Au I ) + L, C 2 Cl 2 2) K 2 C 3, Me Me Me Me anna, I. J. rg. Chem , Liu,. J. Am. Chem. Soc , Chris Wipf Group Page 5 of 14 2/15/2009
6 Au¹ catalyzed cyclopropanation of olefins Tandem cyclopropanation/hydroarylation: formal [4 +3]-annulation Bz 5% Ph 3 PAuCl 5% AgSbF % yield Bz Bz Toste, F. D. J. Am. Chem. Soc , Intermolecular Stereoselective lefin Cyclopropanation Piv 2.5% ()-DTBM-SEGPS(AuCl) 2 5% AgSbF 6 X MeN 2, rt >20:1 cis:trans, 76-94% ee 60-85% yield X Piv Toste, F. D. J. Am. Chem. Soc , Chris Wipf Group Page 6 of 14 2/15/2009
7 Initial Substrate Scope Me 5 mol% Ph 3 PAuCl, 5 mol% AgSbF 6 Me C 2 Cl 2 [0.1 M], rt, 5 min n = 0, = Ac n = 1, = Piv n = 2, = Piv n = 3, = Ac * formation of indene byproducts 10% 99% 99% 44% * Secondary proparglylic esters cyclized in decreased yields for n = 1 and not at all for n = 2. Vinylic substitution generally decreases yield In the presence of 1,1-diphenylethylene, tertiary propargylic esters prefer intramolecular cyclization, where as secondary propargylic esters prefer intermolecular cyclopropanation. Watson, itter, Toste. J. Am. Chem. Soc. ASAP. doi: /ja Chris Wipf Group Page 7 of 14 2/15/2009
8 Intramolecular Enantioselective Cyclopropanation Me Me 5 mol% L*AuCl / AgSbF 6, C 3 N 2 [0.1 M], T, 5 min Entry Ligand T ( C) ee (%) 1 Ac ()-DTBM-SEGPS rt 3 2 Ac ()-xylyl-binap rt 80 3 Piv ()-xylyl-binap rt 49 4 Ac ()-xylyl-binap Entry 1 conditions work well for intermolecular cyclpropanation Ligand screening showed ()-xylyl-binap had best ee Acetate ester showed higher ee than pivaloate (49) and benzoate (63) esters (contrary to intermolecular cyclopropanation). Solvent screening included MeCN (69), C₂Cl₂ (64), CDCl₃ (57), PhMe (20), TF (24), and EtAc (29). Altering the rations of gold to silver has no significant impact on ee (%). Watson, itter, Toste. J. Am. Chem. Soc. ASAP. doi: /ja Chris Wipf Group Page 8 of 14 2/15/2009
9 Intramolecular Enantioselective Cyclopropanation 1 Ac 2.5 mol% ()-xylyl-binap(aucl) 2, 1 Ac 5 mol% AgSbF 6 C 3 N 2, -25 C 2 2 Entry ¹ ² Yield ee (%) 1 Me Et Allyl (C₂)₂Ph * Me Me * L = ()-Difluorophos(AuCl)₂; -25 C Substitution at ¹ is tolerated with out erosion of enantioselectivity In entry 3 preferential 8-member ring formation over 5-member ring. Substitution at ² causes decrease in enantioselectivity and alternate conditions Watson, itter, Toste. J. Am. Chem. Soc. ASAP. doi: /ja Chris Wipf Group Page 9 of 14 2/15/2009
10 Intramolecular Enantioselective Cyclopropanation Me 5 mol% L*AuCl / AgSbF 6, Me C 3 N 2 [0.1 M], T, 5 min Entry Ligand ee (%) 1 Ac ()-xylyl-binap 49 2 Piv ()-xylyl-binap 44 3 Bz ()-xylyl-binap 42 Change in has little effect on ee Various chiral (L*) gold(i) chloride complexes were investigated including ()-BINAP, ()-DTBM-Segphos, and ()-Cl-Me-Biphep giving lower ee Lowering the reaction temperature does not have an impact on enantioselectivity. Much lower ee obtained compared to 8-member ring formation Watson, itter, Toste. J. Am. Chem. Soc. ASAP. doi: /ja Chris Wipf Group Page 10 of 14 2/15/2009
11 Intramolecular Enantioselective Cyclopropanation 5 mol% L*AuCl / AgSbF 6, C 3 N 2 [0.1 M], rt, 5 min Entry Ligand ee (%) 1 Ac ()-Cl-Me-Biphep 37 2 Piv ()-xylyl-binap 85 Various chiral (L*) gold(i) chloride complexes were investigated including ()-BINAP, ()-DTBM-Segphos, and ()-Cl-Me-Biphep (better for Ac, 37) giving decreased enantioselectivity compared to ()-xylyl-binap. Change of has dramatic effect on ee, = Ac (21); Piv (85) No product is isolated a lower temperatures due to decomposition. Watson, itter, Toste. J. Am. Chem. Soc. ASAP. doi: /ja Chris Wipf Group Page 11 of 14 2/15/2009
12 Isomeric Carbeniod Intermediates Piv 5 mol% Ph 3 PAuCl, 5 mol% AgSbF 6 C 2 Cl 2 A Piv AuL 3.6 kcal mol -1 B Piv AuL Ph 47% 90% Ph Piv Piv Ph Ph Selective intramolecular cyclopropanation is observed to form 7- membered ring without 1,1-diphenylethylene In the presence of 1,1-diphenylethylene the intermolecular product occurs exclusively esults indicate that Au(I)-stabilized vinyl carbenoids are fluxional and may even react through the thermodynamically disfavored isomer Watson, itter, Toste. J. Am. Chem. Soc. ASAP. doi: /ja Chris Wipf Group Page 12 of 14 2/15/2009
13 Substrate synthesis Br Br 1) Grignard 2) BuLi, then DMF C 1) Li 2) [] 3) Grignard TMS TMS 1) Deprotection 2) Acylation 1 Commercially available starting material (1-2$ / gram) Straight forward synthesis that allows for various points of derivation Although the reaction does not appear to be tolerant towards complex substitution Chris Wipf Group Page 13 of 14 2/15/2009
14 Conclusion Minor changes in substrate and/or ligand can have profound effects on the result ie. Piv/Ac, 2 vs 3 propargylic esters, and ring size usually involves ligand screening for every substrate The title paper extends the scope of the current methodology by performing asymmetric intramolecular cylopropanation of enynes to form medium sized rings. Supports the notion of the fluxional nature of Au(I) stabilized vinyl carbeniod intermediates Me Me Chris Wipf Group Page 14 of 14 2/15/2009
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