Carbonyl Ylide Cycloadditions
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1 Carbonyl Ylide Cycloadditions cond. icholas Anderson Denmark Group eting 07/13/10
2 Carbonyl Ylides Uncharged 1,3-Dipole Conjugated π-system ighly reactive on-isolable Generate in-situ
3 Carbonyl Ylide Stability Prakash, G. K. S.; Ellis,. W.; Felberg, J. D., lah, G. A. J. Am. Chem. Soc., 1986, 108, D D 2 h! "78 C D D D D D D D D h! - CD 2 - C 2 D D D D
4 Carbonyl Ylide Stability F 3 C F 3 C 2 CF 3 CF h! 2 F 3 C 2 CF 3 F 3 C CF 3 CC of the carbonyl ylide Janulis, E. P.; Arduengo, A. J. J. Am. Chem. Soc., 1983, 105,
5 Electrocyclic Epoxide penings C C C C heat C C C C 1 st order in epoxide 0 th order in styrene C C C rds C C C C C styrene fast C C C C otochemically Allowed Thermally Allowed disrotatory conrotatory uisgen,. Angew. Chem. Int. Ed., 1977, 16,
6 Electrocyclic Epoxide penings 2 C C 2 C C 2 C C 2 C C heat conrot. C C C 2 C 2 C C 2 C C 2 Limitations: requires highly EWG on at least one side of the epoxide uisgen,. Angew. Chem. Int. Ed., 1977, 16,
7 etrocycloadditions - xadiazolines LTA! - 2 1,4-ydride Shift Ar! Ar - 2 Collapse Ar Bekhazi, M.; Warkentin, J. J. Am. Chem. Soc., 1983, 105, Warkentin, J. J. Chem. Soc., Perkin Trans. 1, 2000,
8 etrocycloadditions - xadiazolines C CCl 3 CCl 3 Cl 3 C CCl 3 CCl 3 - Bekhazi, M.; Lawrynowicz, W.; Warkentin, J. Can. J. Chem.-ev. Can. Chim., 1991, 69, Warkentin, J. J. Chem. Soc., Perkin Trans. 1, 2000,
9 etrocycloadditions - xadiazolines 80 C DMAD Benzene = C, Alkyl, Aryl 2 TMS 80 C DMAD Benzene 2 C 2 C TMS Si 3 Si 3 48% TMS TMS TMS 2 C C 2 C 2 C 25% (1:1 dr) 25% (1:1 dr) 7% Sharma, P. K.; Warkentin, J. Tet. Lett., 1995, 36(42),
10 1,3-Elimination of Ethers TMS Cl CsF C DMAD 2 C C 2 2 C C 2 2 C C 2 65% 79% (3:1) C 2 C C 2 43% (59:16:14:11) 81% (1:1 dr) 81% (1:1) ojo, M.; hkuma, M.; Ishibashi,.; osomi, A. Tet. Lett., 1993, 34(37),
11 1,3-Elimination of Ethers (C 2 ) 3 Cl Cl Mn 0, PbCl 2 ai, TF (C 2 ) 2 (C 2 ) 3 76% Bn C 2 (C 2 ) 3 93% 63% 85% 83% ex Ts 79% 78% 98% 73% ojo, M.; et al. J. rg. Chem., 1997, 62,
12 Samarium(II) Iodide diated Carbonyl Ylide Formation TES SmI 2 I TF 17% 33% TES Sm III I TES Sm III TES I - TES Sm III I ' ' ' ' ' ' 64-99% 88-99% 78% 25-40% ojo, M.; Aihara,.; osomi, A., J. Am. Chem. Soc., 1996, 118,
13 Carbonyl Ylides from Carbenes g Cl Br Cl Ar 2 C Benzene, 80 C C 2 Ar Cl C 2 C 2 Cl Cl Ar Ar Cl Cl 2 C C 2 Ar Cl Cl C 2 C 2 g Cl Br Cl Et 2 C C 2 Et Cl Cl C 2 Et C 2 Et Gill,. S.; Landgrebe, J. A. J. rg. Chem., 1983, 48,
14 Diazirine Decomposition Cl acetone,! Ar DMAD Ar Cl 2 Ar 2 C C 2 2 C C 2! DMAD Cl Ar Cl Ar Cl Ar acetone,! Ar Cl 2 Ar Ibata, T.; Liu, M. T..; Toyoda, J. Tet. Lett., 1986, 27,
15 hodium Catalysis h = h 2 (Ac) 4 Padwa, A.; Fryxell, G. E.; Zhi, L., J. Am. Chem. Soc., 1990, 112,
16 Diazocompounds and Amides/Esters 2 h 2 (Ac) 4 taut. DMAD 2 C 2 C Padwa, A.; Stull, P. D., Tet. Lett., 1987, 28(45), Padwa, A.; Zhi, L., J. Am. Chem. Soc., 1990, 112,
17 Diazocompounds and Aldehydes 2 C TMS 2 C h 2 (pfb) 4 C C C 2 TMS C 2 Et 2 C h 2 (Ac) 4 2 C 2 Et C 2 Et Major product Alt, M. Maas, G., Tetrahedron, 1994, 50(25), Wenkert, E.; Khatuya,., Tet. Lett., 1999, 40, 5439 amaguchi, M.; et al., Tet. Lett., 2000, 41,
18 Diazocompounds and Aldehydes 2 C C 2 Cu 0 2 C C C 2 C C 2 C 2 C 2 58% (54:46 dr) C 2 C 2 C 2 C 2 C 2 C 2 C 2 C 2 2 C C 2 24% (55:45 dr) 42% 59% (83:17 dr) 2 C 58% C 2 mass balance was typically epoxide: C 2 C 2 C 2 C 2 C 2 C 2 DMAD 10 days 125 C 2 C C 2 C 2 C 2 uisgen,.; De March, P., J. Am. Chem. Soc., 1982, 104,
19 Diazocompounds and Ketones 25-70%, mixture of isomers 68-85% o isomers observed 50% (1:1 dr) Padwa, A., et al. Tet. Lett., 1989, 30(3),
20 Selectivity ationalization FM can explain selectivity: M dipole LUM dipolarophile for e - poor dipolarophiles LUM dipole M dipolarophile for e- rich dipolarophiles Largest LUM coef. h 2 (Ac) 4 2 Largest M coef. Largest M h 2 (Ac) 4 C 2 C 2 2 Largest LUM Padwa, A., et al. Tet. Lett., 1989, 30(3),
21 Polycycles Through Carbonyl Ylides 66% 85% 72% high yield 88% Padwa, A., et al. Tet. Lett., 1989, 30(3),
22 Increase Complexity 48% Padwa, A., et al. J. rg. Chem., 1991, 56(7),
23 Ligand Effects on Selectivity 2 h h cyclopropanation Padwa, A.; Austin, D. J.; ornbuckle, S. F., J. rg. Chem., 1996, 61,
24 Ligand Effects on Selectivity Ligand affect is unclear owever, ligand IS present during cycloaddition Padwa, A.; Austin, D. J.; ornbuckle, S. F., J. rg. Chem., 1996, 61, Cap = caprolactamate Pfb = perfluorobutyrate Tfa = trifluoroacetate
25 Ligand Effects on Selectivity The more electron poor ligands cause the intermediate carbene to be more electrophilic favoring formation of the carbonyl ylide. Padwa, A.; Austin, D. J.; ornbuckle, S. F., J. rg. Chem., 1996, 61,
26 Enantioselective Carbonyl Ylide Cycloadditions 2 C 2 h 2 (Ligand) 4 DCM, rt Lnh C 2 Et C 2 Et Ligand Yield er Ac 73% 50:50 5-MEPY 75% 50:50 S-DSP 54:46 S-DSP a 76% 76:24 5-MEPY C S 2 Ar Ar= 4-C C 6 4 S-DSP -DDBP a 81% 94:6 P a) run in hexane C DDBP odgson, D. M.; Stupple, P. A.; Johnstone, C., Tet. Lett., 1997, 38(36), odgson, D. M.; et al., J. Chem. Soc., Chem. Commun., 1999,
27 Enantioselective Substrate Scope h 2 (DDBP) 4 63% 82:18 er h 2 (DDBP) 4 77% 87:13 er h 2 (DDBP) 4 67% 88:12 er h 2 (DDBP) 4 76% 80:20 er h 2 (DDBP) 4 73% 93:7 er h 2 (DDBP) 4 41% 86:14 er h 2 (DDBP) 4 44% 75:25 er h 2 (DDBP) 4 38% 83:17 er odgson, D. M.; et al., J. rg. Chem., 2003, 68(16),
28 Asymmetric Cycloadditions from Esters Kitagaki, S.; et al., Tet. Lett., 2000, 41,
29 Asymmetric Induction via a Chiral Lewis Acid Ar = Suga,.; et al., J. rg. Chem., 2005, 70,
30 Asymmetric Induction via Chiral Dipolarophile Top face blocked by p-tol and Et groups uano, J. L. G.; et al., J. rg. Chem., 2006, 71,
31 Applications to Total Synthesis Zaragozic Acid C 13 steps Cond. Conditions: h 2 (Ac) 4 (5 mol%), C CC() (3 equiv), benzene, reflux, 1 h, 72% verall synthesis: 30 steps, 3.7% Carbonyl Ylide Cycloaddition: generates the bicyclic core allows for possible mid stage modifications akamura, S.; et al., Angew. Chem. Int. Ed., 2003, 42,
32 Applications to Total Synthesis (±)-Aspidophytine 10 steps 21 steps, 6.5% overall yield Cabonyl Ylide Cycloaddition: Forms 2 new rings Forms 4 contiguous stereocenters (racemicly) jia-neto, J. M.; Padwa, A., rg. Lett., 2006, 8(15),
33 Applications to Total Synthesis Vindorosine Carbonyl ylide precursor is formed in 4 steps from tryptophan Four new rings are formed, incorporating six contiguous stereocenters Conditions: Triisopropylbenzene 230 o C, 132 h 0.1 mm, 78% yield Elliott, G. I.; et al., Angew. Chem. Int. Ed., 2006, 45,
34 Conclusions and utlook Dipolar carbonyl ylide cycloadditions provide a unique route to highly functionalized di- and tetrahydrofurans hodium catalyzed reactions of diazoketones with carbonyl moieties is the most widely utilized method for formation of carbonyl ylides Systems for generating enatioenriched tetrahydrofurans have been developed More studies on the role of rhodium and the interaction of ligands with the substrate are needed in order to develop more highly enantioselective and general reactions
35 Further eading Padwa, A.; Pearson, W.., Synthetic Applications of 1,3- Dipolar Cycloaddition Chemistry Toward eterocycles and atural Products, Wiley and Sons, 2003 Muthusamy, S.; Krishnamurthi, J., eterocycles by Cycloadditions of Carbonyl Ylides Generated from Diazo Ketones, Springer-Verlag Berlin, 2008 ef., J. Am. Chem. Soc., 1982, 104,
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