Reactivity within Confined Nano-spaces

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1 Reactivity within Confined Nano-spaces Larry Wolf Group Meeting

2 Encapsulating Cyclobutadiene hemicarcerand Anslyn, E. V; Dougherty, D. A. Modern Physical Organic Chemistry Cram. D. J. et. al. Angew. Chem. Int. E. Engl. 1991, 30, 1024

3 Self-Assembled nanocapsules binding outline via Coordination via Hydrogen Bonding via Template-mediated Hydrophobic Effects

4 Rebek s softball synthesis Rebek, J, Jr. et. al. Science, 1995, 270, 1485 Rebek, J, J. et. al. Nature, 1996, 382, 239

5 Softball Welcomes Guests O OH 1.2 equiv B at 343 A 1.2 equiv B at 298 B Host alone in p- xylene at equiv A at 323 K 0.7 equiv A at 273 K Host alone in chloroform-d

6 Template Mediated Self-assembly of a Cavitand Gibb, B. C. J. Am. Chem. Soc.2003, 125, 650

7 Encapsulation C-18 Me shifts to -1.0 ppm Gibb, B. C. J. Am. Chem. Soc.2004, 11408

8 Tetrahedral Anionic Coordination Capsules (Raymond) M 2 L 3 M 4 L 6 Up to 450 Å 3 cavity Raymond, K. N. et. al. Angew. Chem. Int. Ed. 1998, 37, 1840

9 Crystal Structure Representations

10 Encapsulation of Quaternary Ammonium Hosts

11 Cationic Coordination Capsules Fujita, M. et. al. Nature, 1995, 378, 469

12 Encapsulation Experiments 1:1 4 1:2 1:4 1:8 Fujita, M. et. al. Nature, 1995, 378, 469

13 Energy Considerations Reek, J. N. H. et. al. Chem. Soc. Rev. 2008, 37, 247

14 Extremes and Selectivity Consequences Extreme 1: Increase in effective concentration Extreme 2: change in activation parameters ( ) Reek, J. N. H. et. al. Chem. Soc. Rev. 2008, 37, 247

15 Cationic Guests: Making Amines Strong Bases Raymond K. N. ; Bergman, R. B. J. Am. Chem. Soc. 2007, 129, 11459

16 Amine Scope and Encapsulation Data Raymond K. N. ; Bergman, R. B. J. Am. Chem. Soc. 2007, 129, 11459

17 Stabilization of Imminium Ions by Encapsulation Encapsulated imminmium ions remained stable for months at RT Cage 1 has been used to stabilize phosphonium, diazonium ions, & tropylium ions Raymond, K. N.; Bergman R. G. et al. J. Am. Chem. Soc.2006, 128, 14464

18 Acid Catalysis in Basic Solution: Acetal Hydrolysis - Addition of organic solvents decreased the rate of hydrolysis - saturation in substrate is observed - 1 st order in [H+] and [1] - S ǂ = -9 cal mol -1 K -1 - k(h 2 O)/k(D 2 O) = 0.62 Raymond, K. N.; Bergman, R, G. et. al. Angew. Chem. Int. Ed. 2007, 46, 8587 Raymond, K. N.; Bergman, R. G. et. al. J. Org. Chem. 2009, 74, 58

19 Mechanism Rate Accelerations: Raymond, K. N.; Bergman, R. G. et. al. J. Org. Chem. 2009, 74, 58

20 Orthoformate Hydrolysis - S ǂ = -5 cal mol -1 K -1 - S.I.E. = addition of organic solvents led to product inhibition - saturation in substrate - no saturation in [H + ] at 8 < ph < 13 8 < ph < 13 Question(s)? - What is the operative mechanism? - derive the above rate law with 8 < ph <13 - Is the mechanism different than for acetal hydrolysis? Why or why not? Raymond, K. N.; Bergman, R. G. et. al. J. Am. Chem. Soc.2008, 130, 11423

21 Solution Steady-State to resting state: Saturation consequence

22 Michaelis-Menten kinetics R Me Et Pr i-pr Raymond, K. N.; Bergman, R. G. et. al. J. Am. Chem. Soc.2008, 130, 11423

23 Aza-Cope Rearrangment Raymond, K. N.; Bergman, R. G. et. al. Angew. Chem. Int. Ed. 2004, 43, 6748 Raymond, K. N.; Bergman, R. G. et. al. J. Am. Chem. Soc. 2006, 128, 10240

24 Mechanism Solvent Dependence: Eyring Analysis: - No cat: S ǂ = -8 eu, H ǂ = 23.1 kcal/mol - w/ cat: S ǂ = +2 eu, H ǂ = 23.0 kcal/mol - more sterically hindering substrates result in a more pronounced decrease in H ǂ (1-2 kcal/mol) Raymond, K. N.; Bergman, R. G. et. al. J. Am. Chem. Soc. 2006, 128, 10240

25 Cycloadditions ([4+2]) fold acceleration - No reaction with 15a or 2s Rebek, J. Jr. Nature, 1997, 385, 50 Rebek, J. Jr. J. Am. Chem. Soc. 1998, 120, 3650

26 Catalyst Turnover cat 7 bgd 6 Rebek, J. Jr. et. al. J. Am. Chem. Soc. 1998, 120, 7389

27 [4+2] regioselectivity Fujita, M. et. al. Science 2006, 312, 251

28 Crystal structure and Modeling support Fujita, M. et. al. Science 2006, 312, 251

29 [4+2] on Unreactive Substrate 8 Fujita, M. et. al. J. Am. Chem. Soc.2007, 129, 7000

30 [2+2] cycloadditions Before hv After hv After extraction In benzene, anti dimer is favored 21:2 Fujita, M. et. al. Angew. Chem. Int. Ed. 2002, 41, 1347 >98% yield

31 Crystal Structure Fujita, M. et. al. Angew. Chem. Int. Ed. 2002, 41, 1347

32 Cross-Photodimerization [2+2] Fujita, M. et. al. J. Am. Chem. Soc. 2003, 125, 3243

33 Alkane Oxidation Strong absorption at 370 nm Peroxide/alcohol = 4:1 (24%) Fujita, M. et. al. J. Am. Chem. Soc. 2004, 126, 9172 Fujita, M. et. al. J. Am. Chem. Soc. 2009, 131, 4764

34 Selective Singlet Oxygen Oxidation E Gibb, B. G.; Ramamurthy, V. et. al. J. Am. Chem. Soc. 2007, 129, 4132

35 Selectivities Rose bengal

36 Conclusions -The typical nano-space within these vessels ranges from Å 3 which is sufficient for encapsulation of 1 large or a number of small molecules - A nano-reactor may promote any one of the following - rate acceleration - effective concentration - lower activation parameters - novel regio- and chemoselectivities - reactivity with otherwise unreactive substrates - stabilization of highly reactive intermediates - potential enantioselective catalysis where other methods are lacking Reviews: Reek, J. N. H. et. al. Chem. Soc. Rev. 2008, 37, 247 Fujita, M. et. al. Angew. Chem. Int. ed. 2009, 48, 3418

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