X- Ray Crystallography Report Relevant to Chapter 4
2.5 Notes and References
(1) Repka, L. M.; Reisman, S. E. J. Org. Chem. 2013, 78, 12314–12320.
(2) Austin, J. F.; Kim, S.-G.; Sinz, C. J.; Xiao, W.-J.; MacMillan, D. W. C. Proc. Natl.
Acad. Sci. U.S.A. 2004, 101, 5482–5487.
(3) Trost, B. M.; Quancard, J. J. Am. Chem. Soc. 2006, 128, 6314–6315.
(4) Angelini, E.; Balsamini, C.; Bartoccini, F.; Lucarini, S.; Piersanti, G. J. Org. Chem.
2008, 73, 5654–5657.
(5) For applications of chiral biphenols in ligand-accelerated 1,2 and 1,4-addition of allyl, alkenyl, and alkynyl boronates to carbonyls, see: (a) Wu, T. R.; Chong, J. M.
J. Am. Chem. Soc. 2005, 127, 3244–3245. (b) Lou, S.; Moquist, P. N.; Schaus, S. E.
J. Am. Chem. Soc. 2006, 128, 12660–12661. (c) Wu, T. R.; Chong, J. M. J. Am.
Chem. Soc. 2007, 129, 4908–4909. (d) Lou, S.; Moquist, P. N.; Schaus, S. E. J. Am.
Chem. Soc. 2007, 129, 15398–15404. (e) Lou, S.; Schaus, S. E. J. Am. Chem. Soc.
2008, 130, 6922–6923.
(6) (a) Fu, I.; Uang, B.-J. Tetrahedron: Asymmetry 2001, 12, 45–48. (b) Guillarme, S.;
Whiting, A. Synlett 2004, 711–713.
(7) Repka, L. M.; Ni, J.; Reisman, S. E. J. Am. Chem. Soc. 2010, 132, 14418–14420.
(8) Shortly before publication of our report, the Piersanti group published a non- asymmetric version of this reaction: Lucarini, S.; Bartoccini, F.; Battistoni, F.;
Diamantini, G.; Piersanti, G.; Righi, M.; Spadoni, G. Org. Lett. 2010, 12, 3844–
3847.
(9) Massiot, G.; Thepenier, P.; Jacquier, M.-J.; Le Men-Olivier, L.; Delaude, C.
Heterocycles 1989, 29, 1435–1438.
(10) Goodson, J. A.; Henry, T. A. J. Chem. Soc. 1925, 127, 1640.
(11) Mokry, J.; Dubravkova, L.; Sefcovic, P. Experientia 1962, 18, 564–545.
(12) Garro-Helion, F.; Merzouk, A.; Guibe, F. J. Org. Chem. 1993, 58, 6109–6113.
Application to pyrroloindolines: Li, G.; Padwa, A. Org. Lett. 2011, 13, 3767–3769.
(13) Crich, D.; Bruncko, M.; Natarajan, S.; Teo, B. K.; Tocher, D. A. Tetrahedron 1995, 51, 2215–2228.
(14) Mills, J. E.; Maryanoff, C. A.; McComsey, D. F.; Stanzione, R. C.; Scott, L. J. Org.
Chem. 1987, 52, 1857–1859.
(15) (a) Kagan, H. B. Adv. Synth. Catal. 2001, 343, 227–233; (b) Girard, C.; Kagan, H.
B. Angew. Chem. Int. Ed. Engl. 1998, 37, 2922–2959; (c) Blackmond, D. G. Acc.
Chem. Res. 2000, 33, 402–411.
(16) An alternative scenario would involve a moderately selective, enantioselective, irreversible conjugate addition, followed by a highly selective, catalyst-controlled irreversible protonation.
(17) (a) Ishihara, K.; Kaneeda, M.; Yamamoto, H. J. Am. Chem. Soc. 1994, 116, 11179–
11180. (b) Ishihara, K.; Nakamura, S.; Kaneeda, M.; Yamamoto, H. J. Am. Chem.
Soc. 1996, 118, 12854–12855. (c) Ishihara, K.; Kurihara, H.; Yamamoto, H. J. Am.
Chem. Soc. 1996, 118, 3049–3050. (d) Ishihara, K.; Nakashima, D.; Hiraiwa, Y.;
Yamamoto, H. J. Am. Chem. Soc. 2003, 125, 24–25. (e) Rauniyar, V.; Zhai, H.;
Hall, D. G. J. Am. Chem. Soc. 2008, 130, 8481–8490. (f) Yamamoto, H.; Futatsugi, K. Angew. Chem. Int. Ed. Engl. 2005, 44, 1924–1942.
(18) Kieffer, M. E.; Repka, L. M.; Reisman, S. E. J. Am. Chem. Soc. 2012, 134, 5131–
5137.
(19) Ni, J.; Wang, H.; Reisman, S. E. Tetrahedron 2013, 69, 5622–5633.
(20) Tuntiwachwuttikul, P.; Taechowisan, T.; Wanbanjob, A.; Thadaniti, S.; Taylor, W.
C. Tetrahedron 2008, 64, 7583–7586.
(21) Raju, R.; Piggott, A. M.; Huang, X.-C.; Capon, R. J. Org. Lett. 2011, 13, 2770–
2773.
(22) M. Rueping, E. Sugiono, A. Steck, T. Thiessmann. Adv. Synth. Catal. 2010, 352, 281–287.
(23) Wu, T. R.; Shen, L.; Chong, J. M. Org. Lett. 2004, 6, 2701–2704.
(24) Ooi, T.; Kameda, M.; Maruoka, K. J. Am. Chem. Soc. 2003, 125, 5139–5151.
(25) Ito, K.; Takahashi, M.; Hoshino, T.; Nishiki, M.; Ohba, Y. Lett. Org. Chem. 2006, 3, 735.
(26) Jensen, T.; Pedersen, H.; Bang-Andersen, B.; Madsen, R.; Jørgensen, M. Angew.
Chem. Int. Ed. 2008, 47, 888.
(27) van Klink, G. P. M.; de Boer, H. J. R.; Schat, G.; Akkerman, O. S.; Bickelhaupt, F.;
Spek, A. L. Organometallics 2002, 21, 2119.
(28) Petit, S.; Duroc, Y.; Larue, V.; Giglione, Léon, C.; Soulama, C.; Denis, A.; Dardel, F. Meinnel, T.; Artaud, I. ChemMedChem 2009, 4, 261.
(29) Sørensen, U. S.; Pombo-Villar, E. Helv. Chim. Acta. 2004, 87, 82.
(30) Hirose, T.; Sunazuka, T.; Yamamoto, D.; Kojima, N.; Shirahata, T.; Harigaya, Y.;
Kuwajima, I.; Ōmura, S. Tetrahedron 2005, 61, 6015.
(31) Petit, S.; Duroc, Y.; Larue, V.; Giglione, Léon, C.; Soulama, C.; Denis, A.; Dardel, F. Meinnel, T.; Artaud, I. ChemMedChem 2009, 4, 261.
(32) Bajwa, G. S.; Brown, R. K. Can. J. Chem. 1969, 47, 785.
(33) Kira, M.; Hino, T.; Sakurai, H. Tetrahedron Lett. 1989, 30, 1099.
(34) Rodriguez, J. G.; Lafuente, A.; Garcia-Almaraz, P. J. Heterocycl. Chem. 2000, 37, 1281.
(35) Methyl 2-acetamidoacrylate is commercially available, or can be prepared according to Crestey, F.; Collot, V.; Steibing, S.; Rault, S. Synthesis 2006, 20, 3506.
(36) Synthesis of methyl 2-trifluoroacetamidoacrylate: Navarre, L.; Martinez, R.; Genet, J.; Darses, S. J. Am. Chem. Soc. 2008, 130, 6159.
(37) Synthesis of benzyl 2-acetamidoacrylate: Liu, G.; Xin, Z.; Liang, H.; Abad- Zapatero, C.; Hajduk, P. J.; Janowick, D. A.; Szczepankiewicz, B. G.; Pei, Z.;
Hutchins, C. W.; Ballaron, S. J.; Stashko, M. A.; Lubben, T. H.; Berg, C. E.;
Rondinone, C. M.; Trevillyan, J. M.; Jirousek, M. R. J. Med. Chem. 2003, 46, 3437.
(38) Synthesis of benzyl 2-trifluoroacetamidoacrylate: Crossley, M.; Stamford, A. Aust.
J. Chem. 1994, 47, 1695.
(39) Underwood, R.; Prasad, K.; Repic, O.; Hardtmann, G. E. Synth. Commun. 1992, 22, 343.
(40) Pitts, M. R.; Harrison, J. R.; Moody, C. J. J. Chem. Soc., Perkin Trans. 1 2001, 9, 955.
(41) Ferreira, E. Ph.D. Dissertation, California Institute of Technology, 2005.
(42) Odle, R.; Blevins, B.; Ratcliff, M.; Hegedus, L. S. J. Org. Chem. 1980, 45, 2709.
APPENDIX 1
Spectra Relevant to Chapter 2:
Enantioselective Synthesis of Pyrroloindolines by a Formal (3 + 2) Cycloaddition
JN-1-197-col Sample Name: JN-1-197-col Data Collected on: hg3.caltech.edu-mercury300 Archive directory: /home/jni/vnmrsys/data Sample directory: JN-1-197-col FidFile: PROTON01 Pulse Sequence: PROTON (s2pul) Solvent: cdcl3 Data collected on: Jul 19 2010 Temp. 25.0 C / 298.1 K Sample #22, Operator: jni Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.706 sec Width 4810.0 Hz 16 repetitions OBSERVE H1, 300.0862583 MHz DATA PROCESSING FT size 32768 Total time 0 min 45 sec
0.96 1.00 1.01 0.93 3.26 3.42 3.42
ppm12345678910
N Me
MeMe 97c
Appendix 1—Spectra Relevant to Chapter 2 117
JN-1-197 Sample Name: JN-1-197 Data Collected on: indy.caltech.edu-inova500 Archive directory: /home/janeni/vnmrsys/data Sample directory: JN-1-197 FidFile: CARBON01 Pulse Sequence: CARBON (s2pul) Solvent: cdcl3 Data collected on: Jul 19 2010 Temp. 25.0 C / 298.1 K Operator: janeni Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.042 sec Width 31446.5 Hz 3200 repetitions OBSERVE C13, 125.6602406 MHz DECOUPLE H1, 499.7445450 MHz Power 39 dB continuously on WALTZ-16 modulated DATA PROCESSING Line broadening 0.5 Hz FT size 65536 Total time 1 hr, 49 min ppm20406080100120140160180200
N Me
MeMe 97c
Appendix 1—Spectra Relevant to Chapter 2 118
JN-1-183-col2 Sample Name: JN-1-183-col2 Data Collected on: indy.caltech.edu-inova500 Archive directory: /home/janeni/vnmrsys/data Sample directory: JN-1-183-col2 FidFile: PROTON01 Pulse Sequence: PROTON (s2pul) Solvent: cdcl3 Data collected on: Jul 6 2010 Temp. 25.0 C / 298.1 K Operator: janeni Relax. delay 2.000 sec Pulse 45.0 degrees Acq. time 2.048 sec Width 8000.0 Hz 16 repetitions OBSERVE H1, 499.7420500 MHz DATA PROCESSING FT size 32768 Total time 1 min 5 sec
2.03 1.02 1.00 3.32 3.38
ppm12345678910
N Me
MeF 97b
Appendix 1—Spectra Relevant to Chapter 2 119
JN-1-183-col2 Sample Name: JN-1-183-col2 Data Collected on: indy.caltech.edu-inova500 Archive directory: /home/janeni/vnmrsys/data Sample directory: JN-1-183-col2 FidFile: CARBON01 Pulse Sequence: CARBON (s2pul) Solvent: cdcl3 Data collected on: Jul 6 2010 Temp. 25.0 C / 298.1 K Operator: janeni Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.042 sec Width 31446.5 Hz 3200 repetitions OBSERVE C13, 125.6602397 MHz DECOUPLE H1, 499.7445450 MHz Power 39 dB continuously on WALTZ-16 modulated DATA PROCESSING Line broadening 1.0 Hz FT size 65536 Total time 1 hr, 49 min ppm20406080100120140160180200
N Me
MeF 97b
Appendix 1—Spectra Relevant to Chapter 2 120
JN-1-181-col Sample Name: JN-1-181-col Data Collected on: indy.caltech.edu-inova500 Archive directory: /home/janeni/vnmrsys/data Sample directory: JN-1-181-col FidFile: PROTON01 Pulse Sequence: PROTON (s2pul) Solvent: cdcl3 Data collected on: Jun 27 2010 Temp. 25.0 C / 298.1 K Operator: janeni Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 2.048 sec Width 8000.0 Hz 8 repetitions OBSERVE H1, 499.7420505 MHz DATA PROCESSING FT size 32768 Total time 0 min 24 sec
0.93 1.00 1.05 0.97 3.44 3.49
ppm12345678910
N Me
MeBr 97d
Appendix 1—Spectra Relevant to Chapter 2 121
JN-1-181-col Sample Name: JN-1-181-col Data Collected on: indy.caltech.edu-inova500 Archive directory: /home/janeni/vnmrsys/data Sample directory: JN-1-181-col FidFile: CARBON01 Pulse Sequence: CARBON (s2pul) Solvent: cdcl3 Data collected on: Jun 27 2010 Temp. 25.0 C / 298.1 K Operator: janeni Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.042 sec Width 31446.5 Hz 3200 repetitions OBSERVE C13, 125.6602458 MHz DECOUPLE H1, 499.7445450 MHz Power 39 dB continuously on WALTZ-16 modulated DATA PROCESSING Line broadening 0.5 Hz FT size 65536 Total time 1 hr, 49 min ppm20406080100120140160180200
N Me
MeBr 97d
Appendix 1—Spectra Relevant to Chapter 2 122
JN-1-199-col Sample Name: JN-1-199-col Data Collected on: siena.caltech.edu-vnmrs400 Archive directory: /home/jni/vnmrsys/data Sample directory: JN-1-199-col FidFile: PROTON01 Pulse Sequence: PROTON (s2pul) Solvent: cdcl3 Data collected on: Jul 24 2010 Temp. 26.0 C / 299.1 K Sample #11, Operator: jni Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 2.556 sec Width 6410.3 Hz 16 repetitions OBSERVE H1, 399.7942813 MHz DATA PROCESSING FT size 32768 Total time 0 min 57 sec
0.93 1.00 0.98 0.94 0.99 1.01 0.97 2.15 3.20
ppm12345678910
Me
Br N H
Appendix 1—Spectra Relevant to Chapter 2 123
JN-1-199-col Sample Name: JN-1-199-col Data Collected on: siena.caltech.edu-vnmrs400 Archive directory: /home/jni/vnmrsys/data Sample directory: JN-1-199-col FidFile: CARBON01 Pulse Sequence: CARBON (s2pul) Solvent: cdcl3 Data collected on: Jul 24 2010 Temp. 26.0 C / 299.1 K Sample #11, Operator: jni Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.285 sec Width 25510.2 Hz 2000 repetitions OBSERVE C13, 100.5283540 MHz DECOUPLE H1, 399.7962875 MHz Power 39 dB continuously on WALTZ-16 modulated DATA PROCESSING Line broadening 0.5 Hz FT size 65536 Total time 1 hr, 16 min ppm20406080100120140160180200
Me
Br N H
Appendix 1—Spectra Relevant to Chapter 2 124
JN-1-201-col Sample Name: JN-1-201-col Data Collected on: siena.caltech.edu-vnmrs400 Archive directory: /home/jni/vnmrsys/data Sample directory: JN-1-201-col FidFile: PROTON01 Pulse Sequence: PROTON (s2pul) Solvent: cdcl3 Data collected on: Jul 24 2010 Temp. 26.0 C / 299.1 K Sample #12, Operator: jni Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 2.556 sec Width 6410.3 Hz 16 repetitions OBSERVE H1, 399.7942813 MHz DATA PROCESSING FT size 32768 Total time 0 min 57 sec
0.91 1.02 1.00 1.02 1.06 3.47 3.45
ppm12345678910
N H
Me Me
Appendix 1—Spectra Relevant to Chapter 2 125
JN-1-201-col Sample Name: JN-1-201-col Data Collected on: siena.caltech.edu-vnmrs400 Archive directory: /home/jni/vnmrsys/data Sample directory: JN-1-201-col FidFile: CARBON01 Pulse Sequence: CARBON (s2pul) Solvent: cdcl3 Data collected on: Jul 24 2010 Temp. 26.0 C / 299.1 K Sample #12, Operator: jni Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.285 sec Width 25510.2 Hz 4000 repetitions OBSERVE C13, 100.5283515 MHz DECOUPLE H1, 399.7962875 MHz Power 39 dB continuously on WALTZ-16 modulated DATA PROCESSING Line broadening 0.5 Hz FT size 65536 Total time 2 hr, 32 min ppm20406080100120140160180200
N H
Me Me
Appendix 1—Spectra Relevant to Chapter 2 126
JN-1-203-col Sample Name: JN-1-203-col Data Collected on: hg3.caltech.edu-mercury300 Archive directory: /home/jni/vnmrsys/data Sample directory: JN-1-203-col FidFile: PROTON01 Pulse Sequence: PROTON (s2pul) Solvent: cdcl3 Data collected on: Jul 19 2010 Temp. 25.0 C / 298.1 K Sample #21, Operator: jni Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.706 sec Width 4810.0 Hz 16 repetitions OBSERVE H1, 300.0862580 MHz DATA PROCESSING FT size 32768 Total time 0 min 45 sec
1.01 1.00 1.03 0.97 3.40 3.50 3.52
ppm12345678910
N Me
Me Me 97e
Appendix 1—Spectra Relevant to Chapter 2 127
JN-1-203 Sample Name: JN-1-203 Data Collected on: siena.caltech.edu-vnmrs400 Archive directory: /home/jni/vnmrsys/data Sample directory: JN-1-203 FidFile: CARBON01 Pulse Sequence: CARBON (s2pul) Solvent: cdcl3 Data collected on: Jul 19 2010 Temp. 25.0 C / 298.1 K Sample #3, Operator: jni Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.285 sec Width 25510.2 Hz 5000 repetitions OBSERVE C13, 100.5283529 MHz DECOUPLE H1, 399.7962875 MHz Power 39 dB continuously on WALTZ-16 modulated DATA PROCESSING Line broadening 0.5 Hz FT size 65536 Total time 3 hr, 10 min ppm20406080100120140160180200
N Me
Me Me 97e
Appendix 1—Spectra Relevant to Chapter 2 128
LMRIV-N-me-TBStryptophol Sample Name: LMRIV-N-me-TBStryptophol Data Collected on: indy.caltech.edu-inova500 Archive directory: /home/lrepka/vnmrsys/data Sample directory: LMRIV-N-me-TBStryptophol FidFile: PROTON01 Pulse Sequence: PROTON (s2pul) Solvent: cdcl3 Data collected on: Jul 10 2010 Temp. 25.0 C / 298.1 K Operator: lrepka Relax. delay 5.000 sec Pulse 45.0 degrees Acq. time 2.048 sec Width 8000.0 Hz 16 repetitions OBSERVE H1, 499.7420500 MHz DATA PROCESSING FT size 32768 Total time 1 min 53 sec
0.95 0.95 0.98 1.00 0.95 2.00 2.99 2.00 9.14 5.93
ppm12345678910
N Me
OTBS 97f
Appendix 1—Spectra Relevant to Chapter 2 129
LMRIV-N-me-TBStryptophol2 Sample Name: LMRIV-N-me-TBStryptophol2 Data Collected on: indy.caltech.edu-inova500 Archive directory: /home/lrepka/vnmrsys/data Sample directory: LMRIV-N-me-TBStryptophol2 FidFile: CARBON01 Pulse Sequence: CARBON (s2pul) Solvent: cdcl3 Data collected on: Jul 10 2010 Temp. 25.0 C / 298.1 K Operator: lrepka Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.042 sec Width 31446.5 Hz 3500 repetitions OBSERVE C13, 125.6602422 MHz DECOUPLE H1, 499.7445450 MHz Power 39 dB continuously on WALTZ-16 modulated DATA PROCESSING Line broadening 0.5 Hz FT size 65536 Total time 1 hr, 59 min ppm20406080100120140160180200
N Me
OTBS 97f
Appendix 1—Spectra Relevant to Chapter 2 130
LMRIV-291-majordr-hsqc Sample Name: LMRIV-291-majordr-hsqc Data Collected on: siena.caltech.edu-vnmrs400 Archive directory: /home/lrepka/vnmrsys/data Sample directory: LMRIV-291-majordr-hsqc FidFile: PROTON01 Pulse Sequence: PROTON (s2pul) Solvent: cdcl3 Data collected on: Aug 1 2010 Temp. 25.0 C / 298.1 K Sample #2, Operator: lrepka Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 2.556 sec Width 6410.3 Hz 8 repetitions OBSERVE H1, 399.7942797 MHz DATA PROCESSING FT size 32768 Total time 0 min 28 sec
1.05 0.52 0.48 0.52 0.50 0.51 0.49 0.50 0.50 0.51 0.49 1.51 1.51 1.51 1.54 0.57 0.53 1.39 0.65 0.29 1.71 1.48 1.54
ppm12345678910 Plotname:--Notassigned--
Me NN H
OMe O AcMe exo-91 rotameric ratio 1.0:1
Appendix 1—Spectra Relevant to Chapter 2 131
LMRIV-291-majordr-conc Sample Name: LMRIV-291-majordr-conc Data Collected on: siena.caltech.edu-vnmrs400 Archive directory: /home/lrepka/vnmrsys/data Sample directory: LMRIV-291-majordr-conc FidFile: CARBON01 Pulse Sequence: CARBON (s2pul) Solvent: cdcl3 Data collected on: Jul 31 2010 Temp. 25.0 C / 298.1 K Sample #11, Operator: lrepka Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.468 sec Width 22321.4 Hz 3000 repetitions OBSERVE C13, 100.5283980 MHz DECOUPLE H1, 399.7962875 MHz Power 39 dB continuously on WALTZ-16 modulated DATA PROCESSING Line broadening 1.0 Hz FT size 65536 Total time 2 hr, 3 min ppm020406080100120140160180
Me NN H
OMe O AcMe exo-91 rotameric ratio 1.0:1
Appendix 1—Spectra Relevant to Chapter 2 132
LMRIV-291-minordr-hsqc Sample Name: LMRIV-291-minordr-hsqc Data Collected on: siena.caltech.edu-vnmrs400 Archive directory: /home/lrepka/vnmrsys/data Sample directory: LMRIV-291-minordr-hsqc FidFile: PROTON01 Pulse Sequence: PROTON (s2pul) Solvent: cdcl3 Data collected on: Aug 1 2010 Temp. 25.0 C / 298.1 K Sample #3, Operator: lrepka Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 2.556 sec Width 6410.3 Hz 8 repetitions OBSERVE H1, 399.7942813 MHz DATA PROCESSING FT size 32768 Total time 0 min 28 sec
0.26 0.76 0.27 0.72 0.26 0.73 0.26 0.74 0.73 0.27 0.26 0.76 0.80 2.29 2.34 0.86 0.81 2.36 2.36 3.26
ppm12345678910 Plotname:--Notassigned--
Me NN H
OMe O AcMe endo-91 rotameric ratio 3.0:1
Appendix 1—Spectra Relevant to Chapter 2 133
LMRIV-291-minordr Sample Name: LMRIV-291-minordr Data Collected on: siena.caltech.edu-vnmrs400 Archive directory: /home/lrepka/vnmrsys/data Sample directory: LMRIV-291-minordr FidFile: CARBON01 Pulse Sequence: CARBON (s2pul) Solvent: cdcl3 Data collected on: Jul 31 2010 Temp. 25.0 C / 298.1 K Sample #12, Operator: lrepka Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.258 sec Width 26041.7 Hz 14500 repetitions OBSERVE C13, 100.5283574 MHz DECOUPLE H1, 399.7962875 MHz Power 39 dB continuously on WALTZ-16 modulated DATA PROCESSING Line broadening 0.5 Hz FT size 65536 Total time 9 hr, 5 min ppm20406080100120140160180200
Me NN H
OMe O AcMe endo-91 rotameric ratio 3.0:1
Appendix 1—Spectra Relevant to Chapter 2 134
JN-1-131-majordiast Sample Name: JN-1-131-majordiast Data Collected on: siena.caltech.edu-vnmrs400 Archive directory: /home/jni/vnmrsys/data Sample directory: JN-1-131-majordiast FidFile: PROTON01 Pulse Sequence: PROTON (s2pul) Solvent: cdcl3 Data collected on: Aug 5 2010 Temp. 25.0 C / 298.1 K Sample #1, Operator: jni Relax. delay 25.000 sec Pulse 45.0 degrees Acq. time 2.556 sec Width 6410.3 Hz 16 repetitions OBSERVE H1, 399.7943120 MHz DATA PROCESSING FT size 32768 Total time 7 min 21 sec
0.99 1.00 1.00 0.99 0.68 0.27 0.68 0.26 2.95 2.09 0.89 1.00 0.69 0.31 0.87 2.18
ppm12345678910 PltNtid
Me NN H
OMe O TFAMe exo-94 rotameric ratio 2.4:1
Appendix 1—Spectra Relevant to Chapter 2 135
JN-1-131-majordiast Sample Name: JN-1-131-majordiast Data Collected on: siena.caltech.edu-vnmrs400 Archive directory: /home/jni/vnmrsys/data Sample directory: JN-1-131-majordiast FidFile: CARBON01 Pulse Sequence: CARBON (s2pul) Solvent: cdcl3 Data collected on: Aug 5 2010 Temp. 25.0 C / 298.1 K Sample #1, Operator: jni Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.285 sec Width 25510.2 Hz 9700 repetitions OBSERVE C13, 100.5283531 MHz DECOUPLE H1, 399.7962875 MHz Power 39 dB continuously on WALTZ-16 modulated DATA PROCESSING Line broadening 3.0 Hz FT size 65536 Total time 6 hr, 9 min ppm20406080100120140160180200
Me NN H
OMe O TFAMe exo-94 rotameric ratio 2.4:1
Appendix 1—Spectra Relevant to Chapter 2 136
JN-1-131-minordiast3 Sample Name: JN-1-131-minordiast3 Data Collected on: indy.caltech.edu-inova500 Archive directory: /home/janeni/vnmrsys/data Sample directory: JN-1-131-minordiast3 FidFile: PROTON01 Pulse Sequence: PROTON (s2pul) Solvent: cdcl3 Data collected on: Aug 5 2010 Operator: janeni Relax. delay 25.000 sec Pulse 45.0 degrees Acq. time 2.500 sec Width 8000.0 Hz 16 repetitions OBSERVE H1, 499.7420505 MHz DATA PROCESSING Line broadening 0.2 Hz FT size 65536 Total time 7 min 20 sec
1.00 0.11 0.91 0.10 0.90 0.09 0.90 0.90 0.12 0.09 0.90 0.27 2.72 2.77 1.20 1.03 0.14 0.22 3.12
ppm12345678910
Me NN H
OMe O TFAMe endo-94 rotameric ratio 9.0:1
Appendix 1—Spectra Relevant to Chapter 2 137
JN-1-131-minordiast3 Sample Name: JN-1-131-minordiast3 Data Collected on: indy.caltech.edu-inova500 Archive directory: /home/janeni/vnmrsys/data Sample directory: JN-1-131-minordiast3 FidFile: CARBON01 Pulse Sequence: CARBON (s2pul) Solvent: cdcl3 Data collected on: Aug 5 2010 Operator: janeni Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.042 sec Width 31446.5 Hz 11000 repetitions OBSERVE C13, 125.6602406 MHz DECOUPLE H1, 499.7445450 MHz Power 39 dB continuously on WALTZ-16 modulated DATA PROCESSING Line broadening 5.0 Hz FT size 65536 Total time 6 hr, 16 min ppm20406080100120140160180200
Me NN H
OMe O TFAMe endo-94 rotameric ratio 9.0:1
Appendix 1—Spectra Relevant to Chapter 2 138
JN-1-151-major Sample Name: JN-1-151-major Data Collected on: hg3.caltech.edu-mercury300 Archive directory: /home/jni/vnmrsys/data Sample directory: JN-1-151-major FidFile: PROTON01 Pulse Sequence: PROTON (s2pul) Solvent: cdcl3 Data collected on: Jun 24 2010 Temp. 25.0 C / 298.1 K Sample #20, Operator: jni Relax. delay 2.000 sec Pulse 45.0 degrees Acq. time 1.706 sec Width 4810.0 Hz 16 repetitions OBSERVE H1, 300.0862588 MHz DATA PROCESSING FT size 32768 Total time 1 min 1 sec
4.60 1.09 1.02 1.03 1.00 0.52 1.02 1.57 0.64 0.36 1.67 1.52 1.13 1.47 0.61 0.58 1.61 1.52 1.71
ppm12345678910
Me NN H
OBn O AcMe exo-95 rotameric ratio 1.1:1
Appendix 1—Spectra Relevant to Chapter 2 139
JN-1-151 Sample Name: JN-1-151 Data Collected on: siena.caltech.edu-vnmrs400 Archive directory: /home/jni/vnmrsys/data Sample directory: JN-1-151 FidFile: CARBON01 Pulse Sequence: CARBON (s2pul) Solvent: cdcl3 Data collected on: Jun 26 2010 Sample #1, Operator: jni Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.285 sec Width 25510.2 Hz 8500 repetitions OBSERVE C13, 100.5283573 MHz DECOUPLE H1, 399.7962875 MHz Power 39 dB continuously on WALTZ-16 modulated DATA PROCESSING Line broadening 1.0 Hz FT size 65536 Total time 5 hr, 23 min ppm20406080100120140160180200
Me NN H
OBn O AcMe exo-95 rotameric ratio 1.1:1
Appendix 1—Spectra Relevant to Chapter 2 140
JN-1-151-minordiast3 Sample Name: JN-1-151-minordiast3 Data Collected on: indy.caltech.edu-inova500 Archive directory: /home/janeni/vnmrsys/data Sample directory: JN-1-151-minordiast3 FidFile: PROTON01 Pulse Sequence: PROTON (s2pul) Solvent: cdcl3 Data collected on: Aug 4 2010 Operator: janeni Relax. delay 25.000 sec Pulse 45.0 degrees Acq. time 2.500 sec Width 8000.0 Hz 16 repetitions OBSERVE H1, 499.7420463 MHz DATA PROCESSING Line broadening 0.2 Hz FT size 65536 Total time 7 min 20 sec
3.10 0.55 1.53 1.07 0.28 0.76 0.25 0.74 0.24 0.75 0.75 0.25 0.26 0.24 0.25 0.75 0.74 0.76 2.26 0.76 0.76 2.12 2.27 3.04
ppm12345678910
Me NN H
OBn O AcMe endo-95 rotameric ratio 3.0:1
Appendix 1—Spectra Relevant to Chapter 2 141
JN-1-151-minordiast3 Sample Name: JN-1-151-minordiast3 Data Collected on: indy.caltech.edu-inova500 Archive directory: /home/janeni/vnmrsys/data Sample directory: JN-1-151-minordiast3 FidFile: CARBON01 Pulse Sequence: CARBON (s2pul) Solvent: cdcl3 Data collected on: Aug 4 2010 Operator: janeni Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.042 sec Width 31446.5 Hz 13000 repetitions OBSERVE C13, 125.6602444 MHz DECOUPLE H1, 499.7445450 MHz Power 39 dB continuously on WALTZ-16 modulated DATA PROCESSING Line broadening 1.0 Hz FT size 65536 Total time 7 hr, 24 min ppm20406080100120140160180200
Me NN H
OBn O AcMe endo-95 rotameric ratio 3.0:1
Appendix 1—Spectra Relevant to Chapter 2 142
LMRIV-287-majordr-rd25 Sample Name: LMRIV-287-majordr-rd25 Data Collected on: indy.caltech.edu-inova500 Archive directory: /home/lrepka/vnmrsys/data Sample directory: LMRIV-287-majordr-rd25 FidFile: PROTON01 Pulse Sequence: PROTON (s2pul) Solvent: cdcl3 Data collected on: Jul 30 2010 Operator: lrepka Relax. delay 25.000 sec Pulse 45.0 degrees Acq. time 2.500 sec Width 8000.0 Hz 8 repetitions OBSERVE H1, 499.7420490 MHz DATA PROCESSING Line broadening 0.2 Hz FT size 65536 Total time 3 min 40 sec
4.97 0.94 0.28 0.72 0.29 0.71 0.28 0.72 0.70 0.28 1.99 0.70 0.27 2.12 0.84 1.00 0.71 0.28 0.86 2.20
ppm12345678910
Me NN H
OBn O TFAMe exo-96 rotameric ratio 2.6:1
Appendix 1—Spectra Relevant to Chapter 2 143
LMRIV-scale-up-12h-majordr Sample Name: LMRIV-scale-up-12h-majordr Data Collected on: siena.caltech.edu-vnmrs400 Archive directory: /home/lrepka/vnmrsys/data Sample directory: LMRIV-scale-up-12h-majordr FidFile: CARBON01 Pulse Sequence: CARBON (s2pul) Solvent: cdcl3 Data collected on: Jul 29 2010 Temp. 25.0 C / 298.1 K Sample #1, Operator: lrepka Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.285 sec Width 25510.2 Hz 11500 repetitions OBSERVE C13, 100.5283829 MHz DECOUPLE H1, 399.7962875 MHz Power 39 dB continuously on WALTZ-16 modulated DATA PROCESSING Line broadening 0.5 Hz FT size 65536 Total time 7 hr, 17 min ppm20406080100120140160180200
Me NN H
OBn O TFAMe exo-96 rotameric ratio 2.6:1
Appendix 1—Spectra Relevant to Chapter 2 144
LMRIV-287-minor-8-5-10 Sample Name: LMRIV-287-minor-8-5-10 Data Collected on: hg3.caltech.edu-mercury300 Archive directory: /home/lrepka/vnmrsys/data Sample directory: LMRIV-287-minor-8-5-10 FidFile: PROTON01 Pulse Sequence: PROTON (s2pul) Solvent: cdcl3 Data collected on: Aug 5 2010 Temp. 25.0 C / 298.1 K Sample #46, Operator: lrepka Relax. delay 25.000 sec Pulse 45.0 degrees Acq. time 1.706 sec Width 4810.0 Hz 8 repetitions OBSERVE H1, 300.0862322 MHz DATA PROCESSING FT size 32768 Total time 3 min 35 sec
3.06 0.30 2.81 0.15 0.90 0.13 0.87 0.12 0.88 0.89 0.11 0.10 0.10 0.09 0.90 0.89 0.89 2.68 0.92 0.30 0.10 0.92 0.12 2.94
ppm12345678910
Me NN H
OBn O TFAMe endo-96 rotameric ratio 10.0:1
Appendix 1—Spectra Relevant to Chapter 2 145
LMRIV-scale-up-12h-minordr Sample Name: LMRIV-scale-up-12h-minordr Data Collected on: indy.caltech.edu-inova500 Archive directory: /home/lrepka/vnmrsys/data Sample directory: LMRIV-scale-up-12h-minordr FidFile: CARBON01 Pulse Sequence: CARBON (s2pul) Solvent: cdcl3 Data collected on: Jul 29 2010 Operator: lrepka Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.042 sec Width 31446.5 Hz 13500 repetitions OBSERVE C13, 125.6602412 MHz DECOUPLE H1, 499.7445450 MHz Power 39 dB continuously on WALTZ-16 modulated DATA PROCESSING Line broadening 1.0 Hz FT size 65536 Total time 7 hr, 41 min ppm20406080100120140160180200
Me NN H
OBn O TFAMe endo-96 rotameric ratio 10.0:1
Appendix 1—Spectra Relevant to Chapter 2 146
JN-1-191-majordiast Sample Name: JN-1-191-majordiast Data Collected on: siena.caltech.edu-vnmrs400 Archive directory: /home/jni/vnmrsys/data Sample directory: JN-1-191-majordiast FidFile: PROTON01 Pulse Sequence: PROTON (s2pul) Solvent: cdcl3 Data collected on: Jul 19 2010 Temp. 25.0 C / 298.1 K Sample #5, Operator: jni Relax. delay 25.000 sec Pulse 45.0 degrees Acq. time 2.556 sec Width 6410.3 Hz 16 repetitions OBSERVE H1, 399.7942813 MHz DATA PROCESSING FT size 32768 Total time 7 min 21 sec
5.00 0.99 1.00 0.37 0.63 0.61 2.35 0.62 0.34 3.00 1.87 1.09 1.00 0.64 0.52 1.15 2.24
ppm12345678910
Me NN H
OBn O TFAMe exo-98a
MeO rotameric ratio 1.7:1
Appendix 1—Spectra Relevant to Chapter 2 147
JN-1-191-majordiast Sample Name: JN-1-191-majordiast Data Collected on: siena.caltech.edu-vnmrs400 Archive directory: /home/jni/vnmrsys/data Sample directory: JN-1-191-majordiast FidFile: CARBON01 Pulse Sequence: CARBON (s2pul) Solvent: cdcl3 Data collected on: Jul 19 2010 Temp. 25.0 C / 298.1 K Sample #5, Operator: jni Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.285 sec Width 25510.2 Hz 11500 repetitions OBSERVE C13, 100.5283544 MHz DECOUPLE H1, 399.7962875 MHz Power 39 dB continuously on WALTZ-16 modulated DATA PROCESSING Line broadening 1.0 Hz FT size 65536 Total time 7 hr, 17 min ppm20406080100120140160180200
Me NN H
OBn O TFAMe exo-98a
MeO rotameric ratio 1.7:1
Appendix 1—Spectra Relevant to Chapter 2 148
JN-1-191-minordiast Sample Name: JN-1-191-minordiast Data Collected on: indy.caltech.edu-inova500 Archive directory: /home/janeni/vnmrsys/data Sample directory: JN-1-191-minordiast FidFile: PROTON01 Pulse Sequence: PROTON (s2pul) Solvent: cdcl3 Data collected on: Jul 18 2010 Temp. 25.0 C / 298.1 K Operator: janeni Relax. delay 25.000 sec Pulse 45.0 degrees Acq. time 2.500 sec Width 8000.0 Hz 16 repetitions OBSERVE H1, 499.7420505 MHz DATA PROCESSING Line broadening 0.2 Hz FT size 65536 Total time 7 min 20 sec
3.03 0.30 1.75 1.14 0.87 0.14 0.86 0.85 0.15 0.14 0.15 0.14 0.86 0.87 0.86 0.42 2.57 2.57 0.89 0.44 0.16 0.87 0.18 2.52 0.51
ppm12345678910
Me NN H
OBn O TFAMe endo-98a
MeO rotameric ratio 6.0:1
Appendix 1—Spectra Relevant to Chapter 2 149
JN-1-191-minordiast Sample Name: JN-1-191-minordiast Data Collected on: indy.caltech.edu-inova500 Archive directory: /home/janeni/vnmrsys/data Sample directory: JN-1-191-minordiast FidFile: CARBON01 Pulse Sequence: CARBON (s2pul) Solvent: cdcl3 Data collected on: Jul 18 2010 Temp. 25.0 C / 298.1 K Operator: janeni Relax. delay 1.000 sec Pulse 45.0 degrees Acq. time 1.042 sec Width 31446.5 Hz 12000 repetitions OBSERVE C13, 125.6602389 MHz DECOUPLE H1, 499.7445450 MHz Power 39 dB continuously on WALTZ-16 modulated DATA PROCESSING Line broadening 0.5 Hz FT size 65536 Total time 6 hr, 50 min ppm20406080100120140160180200
Me NN H
OBn O TFAMe endo-98a
MeO rotameric ratio 6.0:1
Appendix 1—Spectra Relevant to Chapter 2 150