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FigureLIST OF FIGURESPage1. California Red Scale (Aonidiella aurantii) . . . . . . . 32. California Red Scale Pheromone trap in the field. . . . . . 43. Current commercial reaction scheme of California Red ScalePheromone (3S,6RS)-3-Methyl-6-isopropenyl-9-decen-1-ylAcetate . . . . . . . . . . . . . . . . 64. Proposed New Reaction Scheme of the California Red ScalePheromone (3S,6R)-3-Methyl-6-isopropenyl-9-decen-1-ylAcetate . . . . . . . . . . . . . . . . 85. (S,S) Jacobsen’s catalyst . . . . . . . . . . . . 96. Two step catalytic epoxidation cycle . . . . . . . . . 107. Asymmetric Epoxidation Mechanism . . . . . . . . . 108. Asymmetric epoxidation mechanism applied to citronellyl pivalate 129. (R,R) Jacobsen’s catalyst 3-D top view . . . . . . . . 1310. (R,R) Jacobsen’s catalyst 3-D flat view . . . . . . . . 1311. Citronellyl Pivalate 3-D Structure . . . . . . . . . . 1412. Trans-Alkene approach produces steric repulsion 13-15 . . . . 1513. Tri-substituted alkenes are good substrates for a Jacobsenepoxidation . . . . . . . . . . . . . . . 1614. Partial radical formation during the step-wise addition of oxygen toalkene . . . . . . . . . . . . . . . . . 1615. Ring opening of epoxide by Grignard reagent. . . . . . . 2116. Ring opening of epoxide using Higher Order Cuprates . . . . 2317. IR spectrum of (3S) Citronellyl Pivalate taken as neat sample . . 2518.1 H NMR Spectrum of (3S) Citronellyl Pivalate in CDCl 3 . . . 2619. GC/MS trace of [(3S,6RS)-6,7-Epoxycitronellyl Pivalate] + [(3S)Citronellyl Pivalate] Co-injection (gradient 150 °C → 230 °C,∆T = 5 °C/min) . . . . . . . . . . . . . . 27
viii20. GC/MS trace of (3S) Citronellyl Pivalate (gradient 150 °C → 230°C, ∆T = 5 °C/min), starting material . . . . . . . . 2821. GC/MS trace of (3S,6RS)-6,7-Epoxycitronellyl Pivalate (gradient150 °C → 230 °C, ∆T = 5 °C/min), product . . . . . . 2922.1 H NMR Spectrum of (3S,6RS)-6,7-Epoxycitronellyl Pivalate inCDCl 3 . . . . . . . . . . . . . . . . . 3023. IR Spectrum of (3S,6RS)-6,7-Epoxycitronellyl Pivalate taken asneat sample . . . . . . . . . . . . . . . 3124. GC/MS trace of (3S,6RS)-6,7-Epoxycitronellyl Pivalateisothermal 150 °C. . . . . . . . . . . . . . 3325. GC/MS trace of (3S,6RS)-6,7-Epoxycitronellyl Pivalateisothermal 125 °C . . . . . . . . . . . . . 3426. GC/MS trace of (3S, 6RS)-6,7-Epoxycitronellyl Pivalateisothermal 115 °C . . . . . . . . . . . . . 3527. GC/MS trace of (3S,6RS)-6,7-Epoxycitronellyl acetateisothermal 150 °C . . . . . . . . . . . . . 3628. GC/MS trace of (3S,6RS)-6,7-Epoxycitronellyl acetateisothermal 115 °C . . . . . . . . . . . . . 3729. GC/MS trace of (3S,6RS)-6,7-Epoxycitronellyl acetateisothermal 105 °C . . . . . . . . . . . . . 3830. Integration of GC/MS peak corresponding to(3S,6RS)-6,7-Epoxycitronellyl acetate isothermal 115 °C . . 3931. Integration of GC/MS peak corresponding to(3S,6RS)-6,7-Epoxycitronellyl acetate isothermal 105 °C . . 3932. GC/MS trace of [(3S,6RS)-6,7-Epoxycitronellyl Pivalate]+ [(3S,6S)-6,7-Epoxycitronellyl Pivalate] Co-injection(gradient 150 °C → 230 °C, ∆T = 5 °C/min) . . . . . . 4133.1 H NMR Spectrum of (3S,6RS)-6,7-Epoxycitronellyl Pivalate inCDCl 3 . . . . . . . . . . . . . . . . . 4234. IR Spectrum of (3S,6S)-6,7-Epoxycitronellyl Pivalate taken asneat sample . . . . . . . . . . . . . . . 4235.36.13 C NMR Spectrum of (3S,6RS)-6,7-Epoxycitronellyl Pivalate inCDCl 3 . . . . . . . . . . . . . . . . . 4313 C NMR Spectrum of (3S,6RS)-6,7-Epoxycitronellyl Pivalate(58 ppm – 67 ppm) in CDCl 3 . . . . . . . . . . 44
Page 1: ABSTRACTASYMMETRIC SYNTHESIS OF 6,7
Page 4 and 5: NOTE:THIS PAGE IS OPTIONAL, AND REQ
Page 6 and 7: APPROVEDFor the Department of Chemi
Page 8 and 9: ACKNOWLEDGMENTSI would like to than
Page 12 and 13: 37.38.39.ix13 C NMR Spectrum of (3S
Page 14 and 15: 2support the contention that the fe
Page 16 and 17: Figure 2. California Red Scale pher
Page 18 and 19: 6creation of the chiral center at C
Page 20 and 21: 8During the early 1990s Professor E
Page 22 and 23: 10across the top of the molecule, a
Page 24 and 25: 12molecule and also shows that the
Page 26 and 27: 14Figure 10. (R,R) Jacobsen’s cat
Page 28 and 29: 16stereoselectivity. With tri-subst
Page 30 and 31: 18physical properties (except optic
Page 32 and 33: 20Calo in 1990 published a method o
Page 34 and 35: 22halide into an excess of magnesiu
Page 36 and 37: RESULTS AND DISCUSSIONSynthesis of
Page 38 and 39: Figure 18. 1 H NMR spectrum of (3S)
Page 40 and 41: Figure 20. GC/MS trace of (3S) citr
Page 42 and 43: Figure 22. 1 H NMR spectrum of (3S,
Page 44 and 45: 32IR spectroscopy .Separation of Ep
Page 46 and 47: Figure 25. GC/MS trace of (3S,6RS)-
Page 52 and 53: 40due to the starting material (3S)
Page 54 and 55: 42Figure 33. 1 H NMR spectrum of (3
Page 56 and 57: Figure 36. 13 C NMR spectrum of (3S
Page 58 and 59: 46Figure 37. 13 C NMR Spectrum of (
Page 60 and 61:
48major peak by GC/MS (Figure 40).
Page 62 and 63:
Figure 42. Results of GC/MS library
Page 64 and 65:
52GC/MS trace showed that only inte
Page 66 and 67:
EXPERIMENTALAll 1 H Nuclear Magneti
Page 68 and 69:
56Synthesis of (3S,6RS)-6,7-Epoxyci
Page 70 and 71:
58catalyst in the product. Another
Page 72 and 73:
60was observed and no temperature c
Page 74 and 75:
REFERENCES1. Bodenheimer, F.S. Citr
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