Mechanistic investigations of the palladium-catalyzed aerobic oxidative kinetic resolution of secondary alcohols using (-)-Sparteine

Journal of the American Chemical Society

Volumn 125, Issue 23, 2003, Pages 7005-7013

  Mueller, Jaime A ^a   Sigman, Matthew S ^a  

^a UNIVERSITY OF UTAH   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHIRAL LIGANDS;

ACTIVATION ANALYSIS; ADDITION REACTIONS; CATALYSIS; OXIDATION; REACTION KINETICS; THERMODYNAMICS;

ALCOHOLS;

ALCOHOL DERIVATIVE; PALLADIUM; SPARTEINE;

ADDITION REACTION; ARTICLE; CATALYSIS; CHEMICAL REACTION KINETICS; CHIRALITY; ELIMINATION REACTION; MOLECULAR STABILITY; OXIDATION; PROTON TRANSPORT; STEREOISOMERISM; THERMODYNAMICS;

ALCOHOLS; CATALYSIS; KINETICS; OXIDATION-REDUCTION; PALLADIUM; SPARTEINE; THERMODYNAMICS;

EID: 0038276962     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja034262n     Document Type: Article

References (74)

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9. For examples of Pd(II)-catalyzed aerobic oxidations, see: (a) Schultz, M. J.; Park, C. C.; Sigman, M. S. Chem. Commun. 2002, 3034. (b) Kakiuchi, N.; Maeda, Y.; Nishimura, T.; Uemura, S. J. Org. Chem. 2001, 66, 6620. (c) Hallman, K.; Moberg, C. Adv. Synth. Catal. 2001, 343, 260. (d) ten Brink, G.-J.; Arends, I. W. C. E.; Sheldon, R. A. Science 2000, 287, 1636. (e) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64, 6750. (f) Ebitani, K.; Fujie, Y.; Kaneda, K. Langmuir 1999, 15, 3557. (g) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. Tetrahedron Lett. 1998, 39, 6011. (h) Aït-Mohand, S.; Muzart, J. J. Mol. Catal. A 1998, 129, 135. (i) Peterson, K. P.; Larock, R. C. J. Org. Chem. 1998, 63, 3185. (j) Kaneda, K.; Fujie, Y.; Ebitani, K. Tetrahedron Lett. 1997, 38, 9023. (k) Kaneda, K.; Fujii, M.; Morioka, K. J. Org. Chem. 1996, 61, 4502. (l) Aiet-Mohand, S.; Henin, F.; Muzart, J. Tetrahedron Lett. 1995, 36, 2473. (m) Gómez-Bengoa, E.; Noheda, P.; Echavarren, A. M. Tetrahedron Lett. 1994, 35, 7097. (n) Blackburn, T. F.; Schwartz, J. J. Chem. Soc., Chem. Commun. 1977, 157.
10. For examples of Pd(II)-catalyzed aerobic oxidations, see: (a) Schultz, M. J.; Park, C. C.; Sigman, M. S. Chem. Commun. 2002, 3034. (b) Kakiuchi, N.; Maeda, Y.; Nishimura, T.; Uemura, S. J. Org. Chem. 2001, 66, 6620. (c) Hallman, K.; Moberg, C. Adv. Synth. Catal. 2001, 343, 260. (d) ten Brink, G.-J.; Arends, I. W. C. E.; Sheldon, R. A. Science 2000, 287, 1636. (e) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64, 6750. (f) Ebitani, K.; Fujie, Y.; Kaneda, K. Langmuir 1999, 15, 3557. (g) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. Tetrahedron Lett. 1998, 39, 6011. (h) Aït-Mohand, S.; Muzart, J. J. Mol. Catal. A 1998, 129, 135. (i) Peterson, K. P.; Larock, R. C. J. Org. Chem. 1998, 63, 3185. (j) Kaneda, K.; Fujie, Y.; Ebitani, K. Tetrahedron Lett. 1997, 38, 9023. (k) Kaneda, K.; Fujii, M.; Morioka, K. J. Org. Chem. 1996, 61, 4502. (l) Aiet-Mohand, S.; Henin, F.; Muzart, J. Tetrahedron Lett. 1995, 36, 2473. (m) Gómez-Bengoa, E.; Noheda, P.; Echavarren, A. M. Tetrahedron Lett. 1994, 35, 7097. (n) Blackburn, T. F.; Schwartz, J. J. Chem. Soc., Chem. Commun. 1977, 157.
11. For examples of Pd(II)-catalyzed aerobic oxidations, see: (a) Schultz, M. J.; Park, C. C.; Sigman, M. S. Chem. Commun. 2002, 3034. (b) Kakiuchi, N.; Maeda, Y.; Nishimura, T.; Uemura, S. J. Org. Chem. 2001, 66, 6620. (c) Hallman, K.; Moberg, C. Adv. Synth. Catal. 2001, 343, 260. (d) ten Brink, G.-J.; Arends, I. W. C. E.; Sheldon, R. A. Science 2000, 287, 1636. (e) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64, 6750. (f) Ebitani, K.; Fujie, Y.; Kaneda, K. Langmuir 1999, 15, 3557. (g) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. Tetrahedron Lett. 1998, 39, 6011. (h) Aït-Mohand, S.; Muzart, J. J. Mol. Catal. A 1998, 129, 135. (i) Peterson, K. P.; Larock, R. C. J. Org. Chem. 1998, 63, 3185. (j) Kaneda, K.; Fujie, Y.; Ebitani, K. Tetrahedron Lett. 1997, 38, 9023. (k) Kaneda, K.; Fujii, M.; Morioka, K. J. Org. Chem. 1996, 61, 4502. (l) Aiet-Mohand, S.; Henin, F.; Muzart, J. Tetrahedron Lett. 1995, 36, 2473. (m) Gómez-Bengoa, E.; Noheda, P.; Echavarren, A. M. Tetrahedron Lett. 1994, 35, 7097. (n) Blackburn, T. F.; Schwartz, J. J. Chem. Soc., Chem. Commun. 1977, 157.
12. For examples of Pd(II)-catalyzed aerobic oxidations, see: (a) Schultz, M. J.; Park, C. C.; Sigman, M. S. Chem. Commun. 2002, 3034. (b) Kakiuchi, N.; Maeda, Y.; Nishimura, T.; Uemura, S. J. Org. Chem. 2001, 66, 6620. (c) Hallman, K.; Moberg, C. Adv. Synth. Catal. 2001, 343, 260. (d) ten Brink, G.-J.; Arends, I. W. C. E.; Sheldon, R. A. Science 2000, 287, 1636. (e) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64, 6750. (f) Ebitani, K.; Fujie, Y.; Kaneda, K. Langmuir 1999, 15, 3557. (g) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. Tetrahedron Lett. 1998, 39, 6011. (h) Aït-Mohand, S.; Muzart, J. J. Mol. Catal. A 1998, 129, 135. (i) Peterson, K. P.; Larock, R. C. J. Org. Chem. 1998, 63, 3185. (j) Kaneda, K.; Fujie, Y.; Ebitani, K. Tetrahedron Lett. 1997, 38, 9023. (k) Kaneda, K.; Fujii, M.; Morioka, K. J. Org. Chem. 1996, 61, 4502. (l) Aiet-Mohand, S.; Henin, F.; Muzart, J. Tetrahedron Lett. 1995, 36, 2473. (m) Gómez-Bengoa, E.; Noheda, P.; Echavarren, A. M. Tetrahedron Lett. 1994, 35, 7097. (n) Blackburn, T. F.; Schwartz, J. J. Chem. Soc., Chem. Commun. 1977, 157.
13. For examples of Pd(II)-catalyzed aerobic oxidations, see: (a) Schultz, M. J.; Park, C. C.; Sigman, M. S. Chem. Commun. 2002, 3034. (b) Kakiuchi, N.; Maeda, Y.; Nishimura, T.; Uemura, S. J. Org. Chem. 2001, 66, 6620. (c) Hallman, K.; Moberg, C. Adv. Synth. Catal. 2001, 343, 260. (d) ten Brink, G.-J.; Arends, I. W. C. E.; Sheldon, R. A. Science 2000, 287, 1636. (e) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64, 6750. (f) Ebitani, K.; Fujie, Y.; Kaneda, K. Langmuir 1999, 15, 3557. (g) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. Tetrahedron Lett. 1998, 39, 6011. (h) Aït-Mohand, S.; Muzart, J. J. Mol. Catal. A 1998, 129, 135. (i) Peterson, K. P.; Larock, R. C. J. Org. Chem. 1998, 63, 3185. (j) Kaneda, K.; Fujie, Y.; Ebitani, K. Tetrahedron Lett. 1997, 38, 9023. (k) Kaneda, K.; Fujii, M.; Morioka, K. J. Org. Chem. 1996, 61, 4502. (l) Aiet-Mohand, S.; Henin, F.; Muzart, J. Tetrahedron Lett. 1995, 36, 2473. (m) Gómez-Bengoa, E.; Noheda, P.; Echavarren, A. M. Tetrahedron Lett. 1994, 35, 7097. (n) Blackburn, T. F.; Schwartz, J. J. Chem. Soc., Chem. Commun. 1977, 157.
14. For examples of Pd(II)-catalyzed aerobic oxidations, see: (a) Schultz, M. J.; Park, C. C.; Sigman, M. S. Chem. Commun. 2002, 3034. (b) Kakiuchi, N.; Maeda, Y.; Nishimura, T.; Uemura, S. J. Org. Chem. 2001, 66, 6620. (c) Hallman, K.; Moberg, C. Adv. Synth. Catal. 2001, 343, 260. (d) ten Brink, G.-J.; Arends, I. W. C. E.; Sheldon, R. A. Science 2000, 287, 1636. (e) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64, 6750. (f) Ebitani, K.; Fujie, Y.; Kaneda, K. Langmuir 1999, 15, 3557. (g) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. Tetrahedron Lett. 1998, 39, 6011. (h) Aït-Mohand, S.; Muzart, J. J. Mol. Catal. A 1998, 129, 135. (i) Peterson, K. P.; Larock, R. C. J. Org. Chem. 1998, 63, 3185. (j) Kaneda, K.; Fujie, Y.; Ebitani, K. Tetrahedron Lett. 1997, 38, 9023. (k) Kaneda, K.; Fujii, M.; Morioka, K. J. Org. Chem. 1996, 61, 4502. (l) Aiet-Mohand, S.; Henin, F.; Muzart, J. Tetrahedron Lett. 1995, 36, 2473. (m) Gómez-Bengoa, E.; Noheda, P.; Echavarren, A. M. Tetrahedron Lett. 1994, 35, 7097. (n) Blackburn, T. F.; Schwartz, J. J. Chem. Soc., Chem. Commun. 1977, 157.
15. For examples of Pd(II)-catalyzed aerobic oxidations, see: (a) Schultz, M. J.; Park, C. C.; Sigman, M. S. Chem. Commun. 2002, 3034. (b) Kakiuchi, N.; Maeda, Y.; Nishimura, T.; Uemura, S. J. Org. Chem. 2001, 66, 6620. (c) Hallman, K.; Moberg, C. Adv. Synth. Catal. 2001, 343, 260. (d) ten Brink, G.-J.; Arends, I. W. C. E.; Sheldon, R. A. Science 2000, 287, 1636. (e) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64, 6750. (f) Ebitani, K.; Fujie, Y.; Kaneda, K. Langmuir 1999, 15, 3557. (g) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. Tetrahedron Lett. 1998, 39, 6011. (h) Aït-Mohand, S.; Muzart, J. J. Mol. Catal. A 1998, 129, 135. (i) Peterson, K. P.; Larock, R. C. J. Org. Chem. 1998, 63, 3185. (j) Kaneda, K.; Fujie, Y.; Ebitani, K. Tetrahedron Lett. 1997, 38, 9023. (k) Kaneda, K.; Fujii, M.; Morioka, K. J. Org. Chem. 1996, 61, 4502. (l) Aiet-Mohand, S.; Henin, F.; Muzart, J. Tetrahedron Lett. 1995, 36, 2473. (m) Gómez-Bengoa, E.; Noheda, P.; Echavarren, A. M. Tetrahedron Lett. 1994, 35, 7097. (n) Blackburn, T. F.; Schwartz, J. J. Chem. Soc., Chem. Commun. 1977, 157.
16. For examples of Pd(II)-catalyzed aerobic oxidations, see: (a) Schultz, M. J.; Park, C. C.; Sigman, M. S. Chem. Commun. 2002, 3034. (b) Kakiuchi, N.; Maeda, Y.; Nishimura, T.; Uemura, S. J. Org. Chem. 2001, 66, 6620. (c) Hallman, K.; Moberg, C. Adv. Synth. Catal. 2001, 343, 260. (d) ten Brink, G.-J.; Arends, I. W. C. E.; Sheldon, R. A. Science 2000, 287, 1636. (e) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64, 6750. (f) Ebitani, K.; Fujie, Y.; Kaneda, K. Langmuir 1999, 15, 3557. (g) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. Tetrahedron Lett. 1998, 39, 6011. (h) Aït-Mohand, S.; Muzart, J. J. Mol. Catal. A 1998, 129, 135. (i) Peterson, K. P.; Larock, R. C. J. Org. Chem. 1998, 63, 3185. (j) Kaneda, K.; Fujie, Y.; Ebitani, K. Tetrahedron Lett. 1997, 38, 9023. (k) Kaneda, K.; Fujii, M.; Morioka, K. J. Org. Chem. 1996, 61, 4502. (l) Aiet-Mohand, S.; Henin, F.; Muzart, J. Tetrahedron Lett. 1995, 36, 2473. (m) Gómez-Bengoa, E.; Noheda, P.; Echavarren, A. M. Tetrahedron Lett. 1994, 35, 7097. (n) Blackburn, T. F.; Schwartz, J. J. Chem. Soc., Chem. Commun. 1977, 157.
17. For examples of Pd(II)-catalyzed aerobic oxidations, see: (a) Schultz, M. J.; Park, C. C.; Sigman, M. S. Chem. Commun. 2002, 3034. (b) Kakiuchi, N.; Maeda, Y.; Nishimura, T.; Uemura, S. J. Org. Chem. 2001, 66, 6620. (c) Hallman, K.; Moberg, C. Adv. Synth. Catal. 2001, 343, 260. (d) ten Brink, G.-J.; Arends, I. W. C. E.; Sheldon, R. A. Science 2000, 287, 1636. (e) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64, 6750. (f) Ebitani, K.; Fujie, Y.; Kaneda, K. Langmuir 1999, 15, 3557. (g) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. Tetrahedron Lett. 1998, 39, 6011. (h) Aït-Mohand, S.; Muzart, J. J. Mol. Catal. A 1998, 129, 135. (i) Peterson, K. P.; Larock, R. C. J. Org. Chem. 1998, 63, 3185. (j) Kaneda, K.; Fujie, Y.; Ebitani, K. Tetrahedron Lett. 1997, 38, 9023. (k) Kaneda, K.; Fujii, M.; Morioka, K. J. Org. Chem. 1996, 61, 4502. (l) Aiet-Mohand, S.; Henin, F.; Muzart, J. Tetrahedron Lett. 1995, 36, 2473. (m) Gómez-Bengoa, E.; Noheda, P.; Echavarren, A. M. Tetrahedron Lett. 1994, 35, 7097. (n) Blackburn, T. F.; Schwartz, J. J. Chem. Soc., Chem. Commun. 1977, 157.
18. For examples of Pd(II)-catalyzed aerobic oxidations, see: (a) Schultz, M. J.; Park, C. C.; Sigman, M. S. Chem. Commun. 2002, 3034. (b) Kakiuchi, N.; Maeda, Y.; Nishimura, T.; Uemura, S. J. Org. Chem. 2001, 66, 6620. (c) Hallman, K.; Moberg, C. Adv. Synth. Catal. 2001, 343, 260. (d) ten Brink, G.-J.; Arends, I. W. C. E.; Sheldon, R. A. Science 2000, 287, 1636. (e) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64, 6750. (f) Ebitani, K.; Fujie, Y.; Kaneda, K. Langmuir 1999, 15, 3557. (g) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. Tetrahedron Lett. 1998, 39, 6011. (h) Aït-Mohand, S.; Muzart, J. J. Mol. Catal. A 1998, 129, 135. (i) Peterson, K. P.; Larock, R. C. J. Org. Chem. 1998, 63, 3185. (j) Kaneda, K.; Fujie, Y.; Ebitani, K. Tetrahedron Lett. 1997, 38, 9023. (k) Kaneda, K.; Fujii, M.; Morioka, K. J. Org. Chem. 1996, 61, 4502. (l) Aiet-Mohand, S.; Henin, F.; Muzart, J. Tetrahedron Lett. 1995, 36, 2473. (m) Gómez-Bengoa, E.; Noheda, P.; Echavarren, A. M. Tetrahedron Lett. 1994, 35, 7097. (n) Blackburn, T. F.; Schwartz, J. J. Chem. Soc., Chem. Commun. 1977, 157.
19. For examples of Pd(II)-catalyzed aerobic oxidations, see: (a) Schultz, M. J.; Park, C. C.; Sigman, M. S. Chem. Commun. 2002, 3034. (b) Kakiuchi, N.; Maeda, Y.; Nishimura, T.; Uemura, S. J. Org. Chem. 2001, 66, 6620. (c) Hallman, K.; Moberg, C. Adv. Synth. Catal. 2001, 343, 260. (d) ten Brink, G.-J.; Arends, I. W. C. E.; Sheldon, R. A. Science 2000, 287, 1636. (e) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64, 6750. (f) Ebitani, K.; Fujie, Y.; Kaneda, K. Langmuir 1999, 15, 3557. (g) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. Tetrahedron Lett. 1998, 39, 6011. (h) Aït-Mohand, S.; Muzart, J. J. Mol. Catal. A 1998, 129, 135. (i) Peterson, K. P.; Larock, R. C. J. Org. Chem. 1998, 63, 3185. (j) Kaneda, K.; Fujie, Y.; Ebitani, K. Tetrahedron Lett. 1997, 38, 9023. (k) Kaneda, K.; Fujii, M.; Morioka, K. J. Org. Chem. 1996, 61, 4502. (l) Aiet-Mohand, S.; Henin, F.; Muzart, J. Tetrahedron Lett. 1995, 36, 2473. (m) Gómez-Bengoa, E.; Noheda, P.; Echavarren, A. M. Tetrahedron Lett. 1994, 35, 7097. (n) Blackburn, T. F.; Schwartz, J. J. Chem. Soc., Chem. Commun. 1977, 157.
20. For examples of Pd(II)-catalyzed aerobic oxidations, see: (a) Schultz, M. J.; Park, C. C.; Sigman, M. S. Chem. Commun. 2002, 3034. (b) Kakiuchi, N.; Maeda, Y.; Nishimura, T.; Uemura, S. J. Org. Chem. 2001, 66, 6620. (c) Hallman, K.; Moberg, C. Adv. Synth. Catal. 2001, 343, 260. (d) ten Brink, G.-J.; Arends, I. W. C. E.; Sheldon, R. A. Science 2000, 287, 1636. (e) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64, 6750. (f) Ebitani, K.; Fujie, Y.; Kaneda, K. Langmuir 1999, 15, 3557. (g) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S. Tetrahedron Lett. 1998, 39, 6011. (h) Aït-Mohand, S.; Muzart, J. J. Mol. Catal. A 1998, 129, 135. (i) Peterson, K. P.; Larock, R. C. J. Org. Chem. 1998, 63, 3185. (j) Kaneda, K.; Fujie, Y.; Ebitani, K. Tetrahedron Lett. 1997, 38, 9023. (k) Kaneda, K.; Fujii, M.; Morioka, K. J. Org. Chem. 1996, 61, 4502. (l) Aiet-Mohand, S.; Henin, F.; Muzart, J. Tetrahedron Lett. 1995, 36, 2473. (m) Gómez-Bengoa, E.; Noheda, P.; Echavarren, A. M. Tetrahedron Lett. 1994, 35, 7097. (n) Blackburn, T. F.; Schwartz, J. J. Chem. Soc., Chem. Commun. 1977, 157.
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22. Ferreira, E. M.; Stoltz, B. M. J. Am. Chem. Soc. 2001, 123, 7725.
23. rel = In[(1 - C)(1 - ee)]/ln[(1 - C)(1 + ee)] where C is the conversion and ee is the enantiomeric excess. For an excellent discussion of kinetic resolutions, see: Kagan, H. B.; Fiaud, J. C. Kinetic Resolution. Top. Stereochem. 1988, 18, 249.
24. Alcohols can be resolved by other methods. For catalytic acylation, see: (a) Lin, M.-H.; RajanBabu, T. V. Org. Lett. 2002, 4, 1607. (b) Vedejs, E.; MacKay, J. A. Org. Lett. 2001, 3, 535. (c) Copeland, G. T.; Miller, S. J. J. Am. Chem. Soc. 2001, 123, 6496. (d) Bellemine-Laponnaz, S.; Tweddell, J.; Ruble, J. C.; Breitling, F. M.; Fu, G. C. Chem. Commun. 2000, 1009. (e) Jarvo, E. R.; Copeland, G. T.; Papaioannou, N.; Bonitatebus, P. J., Jr.; Miller, S. J. J. Am. Chem. Soc. 1999, 121, 11638. (f) Vedejs, E.; Daugulis, O. J. Am. Chem. Soc. 1999, 121, 5813. (g) Sano, T.; Imai, K.; Ohashi, K.; Oriyama, T. Chem. Lett. 1999, 265. (h) Miller, S. J.; Copeland, G. T.; Papaioannou, N.; Horstmann, T. E.; Ruel, E. M. J. Am. Chem. Soc. 1998, 120, 1629. (i) Ruble, J. C.; Tweddell, J.; Fu, G. C. J. Org. Chem. 1998, 63, 2794. (j) Ruble, J. C.; Latham, H. A.; Fu, G. C. J. Am. Chem. Soc. 1997, 119, 1492. (k) Kawabata, T.; Nagato, M.; Takasu, K.; Fuji, K. J. Am. Chem. Soc. 1997, 119, 3169. For epoxidation approach: (l) Martin, V. S.; Woodward, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237. Using benzoylation: (m) Iwata, T.; Miyake, Y.; Nishibayashi, Y.; Uemura, S. J. Chem. Soc., Perkin Trans. 1 2002, 13, 1548.
25. Alcohols can be resolved by other methods. For catalytic acylation, see: (a) Lin, M.-H.; RajanBabu, T. V. Org. Lett. 2002, 4, 1607. (b) Vedejs, E.; MacKay, J. A. Org. Lett. 2001, 3, 535. (c) Copeland, G. T.; Miller, S. J. J. Am. Chem. Soc. 2001, 123, 6496. (d) Bellemine-Laponnaz, S.; Tweddell, J.; Ruble, J. C.; Breitling, F. M.; Fu, G. C. Chem. Commun. 2000, 1009. (e) Jarvo, E. R.; Copeland, G. T.; Papaioannou, N.; Bonitatebus, P. J., Jr.; Miller, S. J. J. Am. Chem. Soc. 1999, 121, 11638. (f) Vedejs, E.; Daugulis, O. J. Am. Chem. Soc. 1999, 121, 5813. (g) Sano, T.; Imai, K.; Ohashi, K.; Oriyama, T. Chem. Lett. 1999, 265. (h) Miller, S. J.; Copeland, G. T.; Papaioannou, N.; Horstmann, T. E.; Ruel, E. M. J. Am. Chem. Soc. 1998, 120, 1629. (i) Ruble, J. C.; Tweddell, J.; Fu, G. C. J. Org. Chem. 1998, 63, 2794. (j) Ruble, J. C.; Latham, H. A.; Fu, G. C. J. Am. Chem. Soc. 1997, 119, 1492. (k) Kawabata, T.; Nagato, M.; Takasu, K.; Fuji, K. J. Am. Chem. Soc. 1997, 119, 3169. For epoxidation approach: (l) Martin, V. S.; Woodward, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237. Using benzoylation: (m) Iwata, T.; Miyake, Y.; Nishibayashi, Y.; Uemura, S. J. Chem. Soc., Perkin Trans. 1 2002, 13, 1548.
26. Alcohols can be resolved by other methods. For catalytic acylation, see: (a) Lin, M.-H.; RajanBabu, T. V. Org. Lett. 2002, 4, 1607. (b) Vedejs, E.; MacKay, J. A. Org. Lett. 2001, 3, 535. (c) Copeland, G. T.; Miller, S. J. J. Am. Chem. Soc. 2001, 123, 6496. (d) Bellemine-Laponnaz, S.; Tweddell, J.; Ruble, J. C.; Breitling, F. M.; Fu, G. C. Chem. Commun. 2000, 1009. (e) Jarvo, E. R.; Copeland, G. T.; Papaioannou, N.; Bonitatebus, P. J., Jr.; Miller, S. J. J. Am. Chem. Soc. 1999, 121, 11638. (f) Vedejs, E.; Daugulis, O. J. Am. Chem. Soc. 1999, 121, 5813. (g) Sano, T.; Imai, K.; Ohashi, K.; Oriyama, T. Chem. Lett. 1999, 265. (h) Miller, S. J.; Copeland, G. T.; Papaioannou, N.; Horstmann, T. E.; Ruel, E. M. J. Am. Chem. Soc. 1998, 120, 1629. (i) Ruble, J. C.; Tweddell, J.; Fu, G. C. J. Org. Chem. 1998, 63, 2794. (j) Ruble, J. C.; Latham, H. A.; Fu, G. C. J. Am. Chem. Soc. 1997, 119, 1492. (k) Kawabata, T.; Nagato, M.; Takasu, K.; Fuji, K. J. Am. Chem. Soc. 1997, 119, 3169. For epoxidation approach: (l) Martin, V. S.; Woodward, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237. Using benzoylation: (m) Iwata, T.; Miyake, Y.; Nishibayashi, Y.; Uemura, S. J. Chem. Soc., Perkin Trans. 1 2002, 13, 1548.
27. Alcohols can be resolved by other methods. For catalytic acylation, see: (a) Lin, M.-H.; RajanBabu, T. V. Org. Lett. 2002, 4, 1607. (b) Vedejs, E.; MacKay, J. A. Org. Lett. 2001, 3, 535. (c) Copeland, G. T.; Miller, S. J. J. Am. Chem. Soc. 2001, 123, 6496. (d) Bellemine-Laponnaz, S.; Tweddell, J.; Ruble, J. C.; Breitling, F. M.; Fu, G. C. Chem. Commun. 2000, 1009. (e) Jarvo, E. R.; Copeland, G. T.; Papaioannou, N.; Bonitatebus, P. J., Jr.; Miller, S. J. J. Am. Chem. Soc. 1999, 121, 11638. (f) Vedejs, E.; Daugulis, O. J. Am. Chem. Soc. 1999, 121, 5813. (g) Sano, T.; Imai, K.; Ohashi, K.; Oriyama, T. Chem. Lett. 1999, 265. (h) Miller, S. J.; Copeland, G. T.; Papaioannou, N.; Horstmann, T. E.; Ruel, E. M. J. Am. Chem. Soc. 1998, 120, 1629. (i) Ruble, J. C.; Tweddell, J.; Fu, G. C. J. Org. Chem. 1998, 63, 2794. (j) Ruble, J. C.; Latham, H. A.; Fu, G. C. J. Am. Chem. Soc. 1997, 119, 1492. (k) Kawabata, T.; Nagato, M.; Takasu, K.; Fuji, K. J. Am. Chem. Soc. 1997, 119, 3169. For epoxidation approach: (l) Martin, V. S.; Woodward, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237. Using benzoylation: (m) Iwata, T.; Miyake, Y.; Nishibayashi, Y.; Uemura, S. J. Chem. Soc., Perkin Trans. 1 2002, 13, 1548.
28. Alcohols can be resolved by other methods. For catalytic acylation, see: (a) Lin, M.-H.; RajanBabu, T. V. Org. Lett. 2002, 4, 1607. (b) Vedejs, E.; MacKay, J. A. Org. Lett. 2001, 3, 535. (c) Copeland, G. T.; Miller, S. J. J. Am. Chem. Soc. 2001, 123, 6496. (d) Bellemine-Laponnaz, S.; Tweddell, J.; Ruble, J. C.; Breitling, F. M.; Fu, G. C. Chem. Commun. 2000, 1009. (e) Jarvo, E. R.; Copeland, G. T.; Papaioannou, N.; Bonitatebus, P. J., Jr.; Miller, S. J. J. Am. Chem. Soc. 1999, 121, 11638. (f) Vedejs, E.; Daugulis, O. J. Am. Chem. Soc. 1999, 121, 5813. (g) Sano, T.; Imai, K.; Ohashi, K.; Oriyama, T. Chem. Lett. 1999, 265. (h) Miller, S. J.; Copeland, G. T.; Papaioannou, N.; Horstmann, T. E.; Ruel, E. M. J. Am. Chem. Soc. 1998, 120, 1629. (i) Ruble, J. C.; Tweddell, J.; Fu, G. C. J. Org. Chem. 1998, 63, 2794. (j) Ruble, J. C.; Latham, H. A.; Fu, G. C. J. Am. Chem. Soc. 1997, 119, 1492. (k) Kawabata, T.; Nagato, M.; Takasu, K.; Fuji, K. J. Am. Chem. Soc. 1997, 119, 3169. For epoxidation approach: (l) Martin, V. S.; Woodward, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237. Using benzoylation: (m) Iwata, T.; Miyake, Y.; Nishibayashi, Y.; Uemura, S. J. Chem. Soc., Perkin Trans. 1 2002, 13, 1548.
29. Alcohols can be resolved by other methods. For catalytic acylation, see: (a) Lin, M.-H.; RajanBabu, T. V. Org. Lett. 2002, 4, 1607. (b) Vedejs, E.; MacKay, J. A. Org. Lett. 2001, 3, 535. (c) Copeland, G. T.; Miller, S. J. J. Am. Chem. Soc. 2001, 123, 6496. (d) Bellemine-Laponnaz, S.; Tweddell, J.; Ruble, J. C.; Breitling, F. M.; Fu, G. C. Chem. Commun. 2000, 1009. (e) Jarvo, E. R.; Copeland, G. T.; Papaioannou, N.; Bonitatebus, P. J., Jr.; Miller, S. J. J. Am. Chem. Soc. 1999, 121, 11638. (f) Vedejs, E.; Daugulis, O. J. Am. Chem. Soc. 1999, 121, 5813. (g) Sano, T.; Imai, K.; Ohashi, K.; Oriyama, T. Chem. Lett. 1999, 265. (h) Miller, S. J.; Copeland, G. T.; Papaioannou, N.; Horstmann, T. E.; Ruel, E. M. J. Am. Chem. Soc. 1998, 120, 1629. (i) Ruble, J. C.; Tweddell, J.; Fu, G. C. J. Org. Chem. 1998, 63, 2794. (j) Ruble, J. C.; Latham, H. A.; Fu, G. C. J. Am. Chem. Soc. 1997, 119, 1492. (k) Kawabata, T.; Nagato, M.; Takasu, K.; Fuji, K. J. Am. Chem. Soc. 1997, 119, 3169. For epoxidation approach: (l) Martin, V. S.; Woodward, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237. Using benzoylation: (m) Iwata, T.; Miyake, Y.; Nishibayashi, Y.; Uemura, S. J. Chem. Soc., Perkin Trans. 1 2002, 13, 1548.
30. Alcohols can be resolved by other methods. For catalytic acylation, see: (a) Lin, M.-H.; RajanBabu, T. V. Org. Lett. 2002, 4, 1607. (b) Vedejs, E.; MacKay, J. A. Org. Lett. 2001, 3, 535. (c) Copeland, G. T.; Miller, S. J. J. Am. Chem. Soc. 2001, 123, 6496. (d) Bellemine-Laponnaz, S.; Tweddell, J.; Ruble, J. C.; Breitling, F. M.; Fu, G. C. Chem. Commun. 2000, 1009. (e) Jarvo, E. R.; Copeland, G. T.; Papaioannou, N.; Bonitatebus, P. J., Jr.; Miller, S. J. J. Am. Chem. Soc. 1999, 121, 11638. (f) Vedejs, E.; Daugulis, O. J. Am. Chem. Soc. 1999, 121, 5813. (g) Sano, T.; Imai, K.; Ohashi, K.; Oriyama, T. Chem. Lett. 1999, 265. (h) Miller, S. J.; Copeland, G. T.; Papaioannou, N.; Horstmann, T. E.; Ruel, E. M. J. Am. Chem. Soc. 1998, 120, 1629. (i) Ruble, J. C.; Tweddell, J.; Fu, G. C. J. Org. Chem. 1998, 63, 2794. (j) Ruble, J. C.; Latham, H. A.; Fu, G. C. J. Am. Chem. Soc. 1997, 119, 1492. (k) Kawabata, T.; Nagato, M.; Takasu, K.; Fuji, K. J. Am. Chem. Soc. 1997, 119, 3169. For epoxidation approach: (l) Martin, V. S.; Woodward, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237. Using benzoylation: (m) Iwata, T.; Miyake, Y.; Nishibayashi, Y.; Uemura, S. J. Chem. Soc., Perkin Trans. 1 2002, 13, 1548.
31. Alcohols can be resolved by other methods. For catalytic acylation, see: (a) Lin, M.-H.; RajanBabu, T. V. Org. Lett. 2002, 4, 1607. (b) Vedejs, E.; MacKay, J. A. Org. Lett. 2001, 3, 535. (c) Copeland, G. T.; Miller, S. J. J. Am. Chem. Soc. 2001, 123, 6496. (d) Bellemine-Laponnaz, S.; Tweddell, J.; Ruble, J. C.; Breitling, F. M.; Fu, G. C. Chem. Commun. 2000, 1009. (e) Jarvo, E. R.; Copeland, G. T.; Papaioannou, N.; Bonitatebus, P. J., Jr.; Miller, S. J. J. Am. Chem. Soc. 1999, 121, 11638. (f) Vedejs, E.; Daugulis, O. J. Am. Chem. Soc. 1999, 121, 5813. (g) Sano, T.; Imai, K.; Ohashi, K.; Oriyama, T. Chem. Lett. 1999, 265. (h) Miller, S. J.; Copeland, G. T.; Papaioannou, N.; Horstmann, T. E.; Ruel, E. M. J. Am. Chem. Soc. 1998, 120, 1629. (i) Ruble, J. C.; Tweddell, J.; Fu, G. C. J. Org. Chem. 1998, 63, 2794. (j) Ruble, J. C.; Latham, H. A.; Fu, G. C. J. Am. Chem. Soc. 1997, 119, 1492. (k) Kawabata, T.; Nagato, M.; Takasu, K.; Fuji, K. J. Am. Chem. Soc. 1997, 119, 3169. For epoxidation approach: (l) Martin, V. S.; Woodward, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237. Using benzoylation: (m) Iwata, T.; Miyake, Y.; Nishibayashi, Y.; Uemura, S. J. Chem. Soc., Perkin Trans. 1 2002, 13, 1548.
32. Alcohols can be resolved by other methods. For catalytic acylation, see: (a) Lin, M.-H.; RajanBabu, T. V. Org. Lett. 2002, 4, 1607. (b) Vedejs, E.; MacKay, J. A. Org. Lett. 2001, 3, 535. (c) Copeland, G. T.; Miller, S. J. J. Am. Chem. Soc. 2001, 123, 6496. (d) Bellemine-Laponnaz, S.; Tweddell, J.; Ruble, J. C.; Breitling, F. M.; Fu, G. C. Chem. Commun. 2000, 1009. (e) Jarvo, E. R.; Copeland, G. T.; Papaioannou, N.; Bonitatebus, P. J., Jr.; Miller, S. J. J. Am. Chem. Soc. 1999, 121, 11638. (f) Vedejs, E.; Daugulis, O. J. Am. Chem. Soc. 1999, 121, 5813. (g) Sano, T.; Imai, K.; Ohashi, K.; Oriyama, T. Chem. Lett. 1999, 265. (h) Miller, S. J.; Copeland, G. T.; Papaioannou, N.; Horstmann, T. E.; Ruel, E. M. J. Am. Chem. Soc. 1998, 120, 1629. (i) Ruble, J. C.; Tweddell, J.; Fu, G. C. J. Org. Chem. 1998, 63, 2794. (j) Ruble, J. C.; Latham, H. A.; Fu, G. C. J. Am. Chem. Soc. 1997, 119, 1492. (k) Kawabata, T.; Nagato, M.; Takasu, K.; Fuji, K. J. Am. Chem. Soc. 1997, 119, 3169. For epoxidation approach: (l) Martin, V. S.; Woodward, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237. Using benzoylation: (m) Iwata, T.; Miyake, Y.; Nishibayashi, Y.; Uemura, S. J. Chem. Soc., Perkin Trans. 1 2002, 13, 1548.
33. Alcohols can be resolved by other methods. For catalytic acylation, see: (a) Lin, M.-H.; RajanBabu, T. V. Org. Lett. 2002, 4, 1607. (b) Vedejs, E.; MacKay, J. A. Org. Lett. 2001, 3, 535. (c) Copeland, G. T.; Miller, S. J. J. Am. Chem. Soc. 2001, 123, 6496. (d) Bellemine-Laponnaz, S.; Tweddell, J.; Ruble, J. C.; Breitling, F. M.; Fu, G. C. Chem. Commun. 2000, 1009. (e) Jarvo, E. R.; Copeland, G. T.; Papaioannou, N.; Bonitatebus, P. J., Jr.; Miller, S. J. J. Am. Chem. Soc. 1999, 121, 11638. (f) Vedejs, E.; Daugulis, O. J. Am. Chem. Soc. 1999, 121, 5813. (g) Sano, T.; Imai, K.; Ohashi, K.; Oriyama, T. Chem. Lett. 1999, 265. (h) Miller, S. J.; Copeland, G. T.; Papaioannou, N.; Horstmann, T. E.; Ruel, E. M. J. Am. Chem. Soc. 1998, 120, 1629. (i) Ruble, J. C.; Tweddell, J.; Fu, G. C. J. Org. Chem. 1998, 63, 2794. (j) Ruble, J. C.; Latham, H. A.; Fu, G. C. J. Am. Chem. Soc. 1997, 119, 1492. (k) Kawabata, T.; Nagato, M.; Takasu, K.; Fuji, K. J. Am. Chem. Soc. 1997, 119, 3169. For epoxidation approach: (l) Martin, V. S.; Woodward, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237. Using benzoylation: (m) Iwata, T.; Miyake, Y.; Nishibayashi, Y.; Uemura, S. J. Chem. Soc., Perkin Trans. 1 2002, 13, 1548.
34. Alcohols can be resolved by other methods. For catalytic acylation, see: (a) Lin, M.-H.; RajanBabu, T. V. Org. Lett. 2002, 4, 1607. (b) Vedejs, E.; MacKay, J. A. Org. Lett. 2001, 3, 535. (c) Copeland, G. T.; Miller, S. J. J. Am. Chem. Soc. 2001, 123, 6496. (d) Bellemine-Laponnaz, S.; Tweddell, J.; Ruble, J. C.; Breitling, F. M.; Fu, G. C. Chem. Commun. 2000, 1009. (e) Jarvo, E. R.; Copeland, G. T.; Papaioannou, N.; Bonitatebus, P. J., Jr.; Miller, S. J. J. Am. Chem. Soc. 1999, 121, 11638. (f) Vedejs, E.; Daugulis, O. J. Am. Chem. Soc. 1999, 121, 5813. (g) Sano, T.; Imai, K.; Ohashi, K.; Oriyama, T. Chem. Lett. 1999, 265. (h) Miller, S. J.; Copeland, G. T.; Papaioannou, N.; Horstmann, T. E.; Ruel, E. M. J. Am. Chem. Soc. 1998, 120, 1629. (i) Ruble, J. C.; Tweddell, J.; Fu, G. C. J. Org. Chem. 1998, 63, 2794. (j) Ruble, J. C.; Latham, H. A.; Fu, G. C. J. Am. Chem. Soc. 1997, 119, 1492. (k) Kawabata, T.; Nagato, M.; Takasu, K.; Fuji, K. J. Am. Chem. Soc. 1997, 119, 3169. For epoxidation approach: (l) Martin, V. S.; Woodward, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237. Using benzoylation: (m) Iwata, T.; Miyake, Y.; Nishibayashi, Y.; Uemura, S. J. Chem. Soc., Perkin Trans. 1 2002, 13, 1548.
35. Alcohols can be resolved by other methods. For catalytic acylation, see: (a) Lin, M.-H.; RajanBabu, T. V. Org. Lett. 2002, 4, 1607. (b) Vedejs, E.; MacKay, J. A. Org. Lett. 2001, 3, 535. (c) Copeland, G. T.; Miller, S. J. J. Am. Chem. Soc. 2001, 123, 6496. (d) Bellemine-Laponnaz, S.; Tweddell, J.; Ruble, J. C.; Breitling, F. M.; Fu, G. C. Chem. Commun. 2000, 1009. (e) Jarvo, E. R.; Copeland, G. T.; Papaioannou, N.; Bonitatebus, P. J., Jr.; Miller, S. J. J. Am. Chem. Soc. 1999, 121, 11638. (f) Vedejs, E.; Daugulis, O. J. Am. Chem. Soc. 1999, 121, 5813. (g) Sano, T.; Imai, K.; Ohashi, K.; Oriyama, T. Chem. Lett. 1999, 265. (h) Miller, S. J.; Copeland, G. T.; Papaioannou, N.; Horstmann, T. E.; Ruel, E. M. J. Am. Chem. Soc. 1998, 120, 1629. (i) Ruble, J. C.; Tweddell, J.; Fu, G. C. J. Org. Chem. 1998, 63, 2794. (j) Ruble, J. C.; Latham, H. A.; Fu, G. C. J. Am. Chem. Soc. 1997, 119, 1492. (k) Kawabata, T.; Nagato, M.; Takasu, K.; Fuji, K. J. Am. Chem. Soc. 1997, 119, 3169. For epoxidation approach: (l) Martin, V. S.; Woodward, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237. Using benzoylation: (m) Iwata, T.; Miyake, Y.; Nishibayashi, Y.; Uemura, S. J. Chem. Soc., Perkin Trans. 1 2002, 13, 1548.
36. Alcohols can be resolved by other methods. For catalytic acylation, see: (a) Lin, M.-H.; RajanBabu, T. V. Org. Lett. 2002, 4, 1607. (b) Vedejs, E.; MacKay, J. A. Org. Lett. 2001, 3, 535. (c) Copeland, G. T.; Miller, S. J. J. Am. Chem. Soc. 2001, 123, 6496. (d) Bellemine-Laponnaz, S.; Tweddell, J.; Ruble, J. C.; Breitling, F. M.; Fu, G. C. Chem. Commun. 2000, 1009. (e) Jarvo, E. R.; Copeland, G. T.; Papaioannou, N.; Bonitatebus, P. J., Jr.; Miller, S. J. J. Am. Chem. Soc. 1999, 121, 11638. (f) Vedejs, E.; Daugulis, O. J. Am. Chem. Soc. 1999, 121, 5813. (g) Sano, T.; Imai, K.; Ohashi, K.; Oriyama, T. Chem. Lett. 1999, 265. (h) Miller, S. J.; Copeland, G. T.; Papaioannou, N.; Horstmann, T. E.; Ruel, E. M. J. Am. Chem. Soc. 1998, 120, 1629. (i) Ruble, J. C.; Tweddell, J.; Fu, G. C. J. Org. Chem. 1998, 63, 2794. (j) Ruble, J. C.; Latham, H. A.; Fu, G. C. J. Am. Chem. Soc. 1997, 119, 1492. (k) Kawabata, T.; Nagato, M.; Takasu, K.; Fuji, K. J. Am. Chem. Soc. 1997, 119, 3169. For epoxidation approach: (l) Martin, V. S.; Woodward, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237. Using benzoylation: (m) Iwata, T.; Miyake, Y.; Nishibayashi, Y.; Uemura, S. J. Chem. Soc., Perkin Trans. 1 2002, 13, 1548.
37. For recent oxidative approaches, see: (a) Masutani, K.; Uchida, T.; Irie, R.; Katsuki, T. Tetrahedron Lett. 2000, 41, 5119. (b) Nishibayashi, Y.; Takei, I.; Uemura, S.; Hidai, M. Organometallics 1999, 18, 2291. (c) Gross, Z.; Ini, S. Org Lett. 1999, 1, 2077. (d) Hashiguchi, S.; Fujii, A.; Haack, K.-J.; Matsumura, K.; Ikariya, T.; Noyori, R. Angew. Chem., Int. Ed. Engl. 1997, 36, 288. (e) Rychnovsky, S. D.; McLernon, T. L.; Rajapakse, H. J. Org Chem. 1996, 61, 1194.
38. For recent oxidative approaches, see: (a) Masutani, K.; Uchida, T.; Irie, R.; Katsuki, T. Tetrahedron Lett. 2000, 41, 5119. (b) Nishibayashi, Y.; Takei, I.; Uemura, S.; Hidai, M. Organometallics 1999, 18, 2291. (c) Gross, Z.; Ini, S. Org Lett. 1999, 1, 2077. (d) Hashiguchi, S.; Fujii, A.; Haack, K.-J.; Matsumura, K.; Ikariya, T.; Noyori, R. Angew. Chem., Int. Ed. Engl. 1997, 36, 288. (e) Rychnovsky, S. D.; McLernon, T. L.; Rajapakse, H. J. Org Chem. 1996, 61, 1194.
39. For recent oxidative approaches, see: (a) Masutani, K.; Uchida, T.; Irie, R.; Katsuki, T. Tetrahedron Lett. 2000, 41, 5119. (b) Nishibayashi, Y.; Takei, I.; Uemura, S.; Hidai, M. Organometallics 1999, 18, 2291. (c) Gross, Z.; Ini, S. Org Lett. 1999, 1, 2077. (d) Hashiguchi, S.; Fujii, A.; Haack, K.-J.; Matsumura, K.; Ikariya, T.; Noyori, R. Angew. Chem., Int. Ed. Engl. 1997, 36, 288. (e) Rychnovsky, S. D.; McLernon, T. L.; Rajapakse, H. J. Org Chem. 1996, 61, 1194.
40. For recent oxidative approaches, see: (a) Masutani, K.; Uchida, T.; Irie, R.; Katsuki, T. Tetrahedron Lett. 2000, 41, 5119. (b) Nishibayashi, Y.; Takei, I.; Uemura, S.; Hidai, M. Organometallics 1999, 18, 2291. (c) Gross, Z.; Ini, S. Org Lett. 1999, 1, 2077. (d) Hashiguchi, S.; Fujii, A.; Haack, K.-J.; Matsumura, K.; Ikariya, T.; Noyori, R. Angew. Chem., Int. Ed. Engl. 1997, 36, 288. (e) Rychnovsky, S. D.; McLernon, T. L.; Rajapakse, H. J. Org Chem. 1996, 61, 1194.
41. For recent oxidative approaches, see: (a) Masutani, K.; Uchida, T.; Irie, R.; Katsuki, T. Tetrahedron Lett. 2000, 41, 5119. (b) Nishibayashi, Y.; Takei, I.; Uemura, S.; Hidai, M. Organometallics 1999, 18, 2291. (c) Gross, Z.; Ini, S. Org Lett. 1999, 1, 2077. (d) Hashiguchi, S.; Fujii, A.; Haack, K.-J.; Matsumura, K.; Ikariya, T.; Noyori, R. Angew. Chem., Int. Ed. Engl. 1997, 36, 288. (e) Rychnovsky, S. D.; McLernon, T. L.; Rajapakse, H. J. Org Chem. 1996, 61, 1194.
42. When this transformation is run in open air, significant catalyst decomposition is observed.
43. A total synthesis of (+)-sparteine was reported recently, but it is not yet practical, see: Smith, B. T.; Wendt, J. A.; Aube, J. Org. Lett. 2002, 4, 2577-2579.
44. This Pd(II)/(-)-sparteine-catalyzed OKR has been reported in the synthesis of pharmaceuticals where they used a Mitsunobu inversion to access the other needed enantiomer of alcohol, see: Ali, I. S.; Sudalai, A. Tetrahedron Lett. 2002, 43, 5435.
45. rel values, see: Dearden, M. J.; Firkin, C. R.; Hermet, J.-P. R.; O'Brien, P. J. Am. Chem. Soc. 2002, 124, 11870.
46. Steinhoff, B. A.; Fix, S. R.; Stahl, S. S. Org. Lett. 2002, 4, 4179.
47. ten Brink, G.-J.; Arends, I. W. C. E.; Sheldon, R. A. Adv. Synth. Catal. 2002, 344, 355.
48. Mueller, J. A.; Jensen, D. R.; Sigman, M. S. J. Am. Chem. Soc. 2002, 124, 8202.
49. For a study of Pd(II)-catalyzed oxidation of alcohols in DMSO with rate-limiting catalyst turnover, see: Steinhoff, B. A.; Fix, S. R.; Stahl, S. S. J. Am. Chem. Soc. 2002, 124, 766.
50. For mechanistic insight into the oxygenation of Pd(0)/bathocuproine, see: Stahl, S. S.; Thorman, J. L.; Nelson, R. C.; Kozee, M. A. J. Am. Chem. Soc. 2001, 123, 7188.
51. 2 X-ray crystal analysis.
52. 2. at 65 °C.
53. See Supporting Information for the plots and data analysis.
54. Four reactions were analyzed simultaneously under the same reaction conditions (oxygen atmosphere and temperature fluctuations). See Supporting Information for apparatus. Conditions were slowed from the optimized synthetic conditions to enable the hand sampling of all four reactions.
55. obs = k′[(-)-sparteine]/(k″ + [(-)-sparteine]). For the Michaelis-Menten equation, see: Walsh, C. Enzymatic Reaction Mechanisms; W. H. Freeman and Company: New York, 1979.
56. In these studies, 4 mol % (-)-sparteine is used as low base concentration conditions, and 50 mol % is used as saturating conditions.
57. For derivation of the rate law, see Supporting Information.
58. obs = k′/(k″ + [(-)-sparteine HCI]), where k′ and k″ are constants. See Supporting Information for the statistical analysis.
59. Ozawa, F.; Ito, T.; Yamamoto, A. J. Am. Chem. Soc. 1980, 102, 6457.
60. 8 metals have been reported in which β-hydride elimination has been implicated as the rate-determining step, see: (a) Evans, J.; Schwarts, J.; Urquhart, P. W. J. Organomet. Chem. 1974, 81, C37. (b) Ikariya, T.; Yamamoto, A. Organomet. Chem. 1976, 120, 257.
61. 8 metals have been reported in which β-hydride elimination has been implicated as the rate-determining step, see: (a) Evans, J.; Schwarts, J.; Urquhart, P. W. J. Organomet. Chem. 1974, 81, C37. (b) Ikariya, T.; Yamamoto, A. Organomet. Chem. 1976, 120, 257.
62. These experiments were performed using in situ IR to measure the initial rates of formation of the aldehyde products. The initial absorbencies were measured and converted to concentration of aldehyde product using the Beer-Lambert relationship. Low [(-)-sparteine] is 2 mol % for studies using in situ IR.
63. Lowry, T. H.; Richardson, K. S. Mechanism and Theory in Organic Chemistry, 3rd ed.; Harper and Row: New York, 1987; p 144.
64. For these studies, 2 mol % (-)-sparteine is used for low base concentration conditions, and 50 mol % (-)-sparteine is used for saturation conditions.
65. p-Nitrobenzyl alcohol formed the aldehyde initially, but then formed another side product. Because of the determination of the rate by aldehyde formation, this substrate was not used for the Hammett plot at low [(-)-sparteine].
66. For oxidations using benzyl alcohol. 15 mol % (-)-sparteine is suitable for saturation.
67. (-)-Sparteine has been used to thermodynamically resolve tertiary acetylenic alcohols, see: Toda, F.; Tanaka, K.; Ueda, H.; Oshima, T. J. Chem. Soc., Chem. Commun. 1983, 743.
68. 2.
69. Curtin, D. Y. Rec. Chem. Prog. 1954, 15, 111.
70. For a manifestation of the Curtin-Hammett principle in which the minor diastereomeric adduct gives rise to the major enantiomer of product, see: Halpern, J. Science 1982, 217, 401.
71. a = 1.8 in DMSO).
72. rel values using tert-butyl alcohol as a solvent. Mandal, S. K.; Jensen, D. R.; Pugsley, J. P.; Sigman, M. S. J. Org. Chem. 2003, ASAP.
73. Jensen, D. R.; Sigman, M. S. Org. Lett. 2003, 5, 63.
74. Lewis, E. S.; Funderburk, L. J. Am. Chem. Soc. 1967, 89, 2322.