Enantioselective synthesis of propargylamines through Zr-catalyzed addition of mixed alkynylzinc reagents to arylimines

Organic Letters

Volumn 5, Issue 18, 2003, Pages 3273-3275

  Traverse, John F ^a   Hoveyda, Amir H ^a   Snapper, Marc L ^a  

^a BOSTON COLLEGE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; IMINE; PROPARGYLAMINE; UNCLASSIFIED DRUG; ZINC DERIVATIVE; ZIRCONIUM;

ACYLATION; ARTICLE; CATALYSIS; ENANTIOSELECTIVITY; OXIDATION; SYNTHESIS;

ACYLATION; ALKYNES; AMINO ACIDS; ANILINE COMPOUNDS; CATALYSIS; IMINES; LIGANDS; OXIDATION-REDUCTION; PARGYLINE; PROPYLAMINES; STEREOISOMERISM; ZIRCONIUM;

EID: 0141744680     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol035138b     Document Type: Article

References (41)

1. For representative examples, see: (a) Cole, B. M.; Shimizu, K. D.; Krueger, C. A.; Harrity, J. P.; Snapper, M. L.; Hoveyda, A. H. Angew. Chem., Int. Ed. Engl. 1996, 35, 1668-1671. (b) Krueger, C. A.; Kuntz, K. W.; Dzierba, C. D.; Wirschun, W. G.; Gleason, J. D.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 4284-4285. (c) Degrado, S. J.; Mizutani, H.; Hoveyda, A. H. J. Am. Chem. Soc. 2001, 123, 755-756. (d) Luchaco-Cullis, C. A.; Mizutani, H.; Murphy, K. E.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2001, 40, 1456-1460. (e) Deng, H.; Isler, M. P.; Snapper, M. L.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2002, 41, 1009-1012. (f) Luchaco-Cullis, C. A.; Hoveyda, A. H. J. Am. Chem. Soc. 2002, 124, 8192-8193. (g) Josephsohn, N. S.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 4018-4019. (h) Murphy, K. E.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 4690-4691.
2. For representative examples, see: (a) Cole, B. M.; Shimizu, K. D.; Krueger, C. A.; Harrity, J. P.; Snapper, M. L.; Hoveyda, A. H. Angew. Chem., Int. Ed. Engl. 1996, 35, 1668-1671. (b) Krueger, C. A.; Kuntz, K. W.; Dzierba, C. D.; Wirschun, W. G.; Gleason, J. D.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 4284-4285. (c) Degrado, S. J.; Mizutani, H.; Hoveyda, A. H. J. Am. Chem. Soc. 2001, 123, 755-756. (d) Luchaco-Cullis, C. A.; Mizutani, H.; Murphy, K. E.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2001, 40, 1456-1460. (e) Deng, H.; Isler, M. P.; Snapper, M. L.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2002, 41, 1009-1012. (f) Luchaco-Cullis, C. A.; Hoveyda, A. H. J. Am. Chem. Soc. 2002, 124, 8192-8193. (g) Josephsohn, N. S.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 4018-4019. (h) Murphy, K. E.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 4690-4691.
3. For representative examples, see: (a) Cole, B. M.; Shimizu, K. D.; Krueger, C. A.; Harrity, J. P.; Snapper, M. L.; Hoveyda, A. H. Angew. Chem., Int. Ed. Engl. 1996, 35, 1668-1671. (b) Krueger, C. A.; Kuntz, K. W.; Dzierba, C. D.; Wirschun, W. G.; Gleason, J. D.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 4284-4285. (c) Degrado, S. J.; Mizutani, H.; Hoveyda, A. H. J. Am. Chem. Soc. 2001, 123, 755-756. (d) Luchaco-Cullis, C. A.; Mizutani, H.; Murphy, K. E.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2001, 40, 1456-1460. (e) Deng, H.; Isler, M. P.; Snapper, M. L.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2002, 41, 1009-1012. (f) Luchaco-Cullis, C. A.; Hoveyda, A. H. J. Am. Chem. Soc. 2002, 124, 8192-8193. (g) Josephsohn, N. S.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 4018-4019. (h) Murphy, K. E.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 4690-4691.
4. For representative examples, see: (a) Cole, B. M.; Shimizu, K. D.; Krueger, C. A.; Harrity, J. P.; Snapper, M. L.; Hoveyda, A. H. Angew. Chem., Int. Ed. Engl. 1996, 35, 1668-1671. (b) Krueger, C. A.; Kuntz, K. W.; Dzierba, C. D.; Wirschun, W. G.; Gleason, J. D.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 4284-4285. (c) Degrado, S. J.; Mizutani, H.; Hoveyda, A. H. J. Am. Chem. Soc. 2001, 123, 755-756. (d) Luchaco-Cullis, C. A.; Mizutani, H.; Murphy, K. E.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2001, 40, 1456-1460. (e) Deng, H.; Isler, M. P.; Snapper, M. L.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2002, 41, 1009-1012. (f) Luchaco-Cullis, C. A.; Hoveyda, A. H. J. Am. Chem. Soc. 2002, 124, 8192-8193. (g) Josephsohn, N. S.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 4018-4019. (h) Murphy, K. E.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 4690-4691.
5. For representative examples, see: (a) Cole, B. M.; Shimizu, K. D.; Krueger, C. A.; Harrity, J. P.; Snapper, M. L.; Hoveyda, A. H. Angew. Chem., Int. Ed. Engl. 1996, 35, 1668-1671. (b) Krueger, C. A.; Kuntz, K. W.; Dzierba, C. D.; Wirschun, W. G.; Gleason, J. D.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 4284-4285. (c) Degrado, S. J.; Mizutani, H.; Hoveyda, A. H. J. Am. Chem. Soc. 2001, 123, 755-756. (d) Luchaco-Cullis, C. A.; Mizutani, H.; Murphy, K. E.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2001, 40, 1456-1460. (e) Deng, H.; Isler, M. P.; Snapper, M. L.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2002, 41, 1009-1012. (f) Luchaco-Cullis, C. A.; Hoveyda, A. H. J. Am. Chem. Soc. 2002, 124, 8192-8193. (g) Josephsohn, N. S.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 4018-4019. (h) Murphy, K. E.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 4690-4691.
6. For representative examples, see: (a) Cole, B. M.; Shimizu, K. D.; Krueger, C. A.; Harrity, J. P.; Snapper, M. L.; Hoveyda, A. H. Angew. Chem., Int. Ed. Engl. 1996, 35, 1668-1671. (b) Krueger, C. A.; Kuntz, K. W.; Dzierba, C. D.; Wirschun, W. G.; Gleason, J. D.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 4284-4285. (c) Degrado, S. J.; Mizutani, H.; Hoveyda, A. H. J. Am. Chem. Soc. 2001, 123, 755-756. (d) Luchaco-Cullis, C. A.; Mizutani, H.; Murphy, K. E.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2001, 40, 1456-1460. (e) Deng, H.; Isler, M. P.; Snapper, M. L.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2002, 41, 1009-1012. (f) Luchaco-Cullis, C. A.; Hoveyda, A. H. J. Am. Chem. Soc. 2002, 124, 8192-8193. (g) Josephsohn, N. S.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 4018-4019. (h) Murphy, K. E.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 4690-4691.
7. For representative examples, see: (a) Cole, B. M.; Shimizu, K. D.; Krueger, C. A.; Harrity, J. P.; Snapper, M. L.; Hoveyda, A. H. Angew. Chem., Int. Ed. Engl. 1996, 35, 1668-1671. (b) Krueger, C. A.; Kuntz, K. W.; Dzierba, C. D.; Wirschun, W. G.; Gleason, J. D.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 4284-4285. (c) Degrado, S. J.; Mizutani, H.; Hoveyda, A. H. J. Am. Chem. Soc. 2001, 123, 755-756. (d) Luchaco-Cullis, C. A.; Mizutani, H.; Murphy, K. E.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2001, 40, 1456-1460. (e) Deng, H.; Isler, M. P.; Snapper, M. L.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2002, 41, 1009-1012. (f) Luchaco-Cullis, C. A.; Hoveyda, A. H. J. Am. Chem. Soc. 2002, 124, 8192-8193. (g) Josephsohn, N. S.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 4018-4019. (h) Murphy, K. E.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 4690-4691.
8. For representative examples, see: (a) Cole, B. M.; Shimizu, K. D.; Krueger, C. A.; Harrity, J. P.; Snapper, M. L.; Hoveyda, A. H. Angew. Chem., Int. Ed. Engl. 1996, 35, 1668-1671. (b) Krueger, C. A.; Kuntz, K. W.; Dzierba, C. D.; Wirschun, W. G.; Gleason, J. D.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 4284-4285. (c) Degrado, S. J.; Mizutani, H.; Hoveyda, A. H. J. Am. Chem. Soc. 2001, 123, 755-756. (d) Luchaco-Cullis, C. A.; Mizutani, H.; Murphy, K. E.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2001, 40, 1456-1460. (e) Deng, H.; Isler, M. P.; Snapper, M. L.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2002, 41, 1009-1012. (f) Luchaco-Cullis, C. A.; Hoveyda, A. H. J. Am. Chem. Soc. 2002, 124, 8192-8193. (g) Josephsohn, N. S.; Snapper, M. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 4018-4019. (h) Murphy, K. E.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 4690-4691.
9. For reviews on catalytic asymmetric additions to imines, see: (a) Enders, D.; Reinhold, U. Tetrahedron: Asymmetry 1997, 8, 1895-1946. (b) Kobayashi, S.; Ishitani, H. Chem. Rev. 1999, 99, 1069-1094.
10. For reviews on catalytic asymmetric additions to imines, see: (a) Enders, D.; Reinhold, U. Tetrahedron: Asymmetry 1997, 8, 1895-1946. (b) Kobayashi, S.; Ishitani, H. Chem. Rev. 1999, 99, 1069-1094.
11. (a) Porter, J. R.; Traverse, J. F.; Hoveyda, A. H.; Snapper, M. L. J. Am. Chem. Soc. 2001, 123, 984-985.
12. For related studies involving catalytic asymmetric alkylations of imines, see: (b) Denmark, S. E.; Stiff, C. M. J. Org. Chem. 2000, 65, 5875-5878 and references therein. (c) Fujihara, H.; Nagai, K.; Tomioka, K. J. Am. Chem. Soc. 2000, 122, 12055-12056. (d) Zhang, X.-M.; Zhang, H.-L.; Lin, W.-Q.; Gong, L.-Z. ; Mi, A.-Q.; Cui, X.; Jiang, Y.-Z.; Yu, K.-B. J. Org. Chem. 2003, 68, 4322-4330. (e) Dahmen, S.; Brase, S. J. Am. Chem. Soc. 2002, 124, 5940-5941. (f) Boezio, A. A.; Charrette, A. B. J. Am. Chem. Soc. 2003, 125, 1692-1693.
13. For related studies involving catalytic asymmetric alkylations of imines, see: (b) Denmark, S. E.; Stiff, C. M. J. Org. Chem. 2000, 65, 5875-5878 and references therein. (c) Fujihara, H.; Nagai, K.; Tomioka, K. J. Am. Chem. Soc. 2000, 122, 12055-12056. (d) Zhang, X.-M.; Zhang, H.-L.; Lin, W.-Q.; Gong, L.-Z. ; Mi, A.-Q.; Cui, X.; Jiang, Y.-Z.; Yu, K.-B. J. Org. Chem. 2003, 68, 4322-4330. (e) Dahmen, S.; Brase, S. J. Am. Chem. Soc. 2002, 124, 5940-5941. (f) Boezio, A. A.; Charrette, A. B. J. Am. Chem. Soc. 2003, 125, 1692-1693.
14. For related studies involving catalytic asymmetric alkylations of imines, see: (b) Denmark, S. E.; Stiff, C. M. J. Org. Chem. 2000, 65, 5875-5878 and references therein. (c) Fujihara, H.; Nagai, K.; Tomioka, K. J. Am. Chem. Soc. 2000, 122, 12055-12056. (d) Zhang, X.-M.; Zhang, H.-L.; Lin, W.-Q.; Gong, L.-Z. ; Mi, A.-Q.; Cui, X.; Jiang, Y.-Z.; Yu, K.-B. J. Org. Chem. 2003, 68, 4322-4330. (e) Dahmen, S.; Brase, S. J. Am. Chem. Soc. 2002, 124, 5940-5941. (f) Boezio, A. A.; Charrette, A. B. J. Am. Chem. Soc. 2003, 125, 1692-1693.
15. For related studies involving catalytic asymmetric alkylations of imines, see: (b) Denmark, S. E.; Stiff, C. M. J. Org. Chem. 2000, 65, 5875-5878 and references therein. (c) Fujihara, H.; Nagai, K.; Tomioka, K. J. Am. Chem. Soc. 2000, 122, 12055-12056. (d) Zhang, X.-M.; Zhang, H.-L.; Lin, W.-Q.; Gong, L.-Z. ; Mi, A.-Q.; Cui, X.; Jiang, Y.-Z.; Yu, K.-B. J. Org. Chem. 2003, 68, 4322-4330. (e) Dahmen, S.; Brase, S. J. Am. Chem. Soc. 2002, 124, 5940-5941. (f) Boezio, A. A.; Charrette, A. B. J. Am. Chem. Soc. 2003, 125, 1692-1693.
16. For related studies involving catalytic asymmetric alkylations of imines, see: (b) Denmark, S. E.; Stiff, C. M. J. Org. Chem. 2000, 65, 5875-5878 and references therein. (c) Fujihara, H.; Nagai, K.; Tomioka, K. J. Am. Chem. Soc. 2000, 122, 12055-12056. (d) Zhang, X.-M.; Zhang, H.-L.; Lin, W.-Q.; Gong, L.-Z. ; Mi, A.-Q.; Cui, X.; Jiang, Y.-Z.; Yu, K.-B. J. Org. Chem. 2003, 68, 4322-4330. (e) Dahmen, S.; Brase, S. J. Am. Chem. Soc. 2002, 124, 5940-5941. (f) Boezio, A. A.; Charrette, A. B. J. Am. Chem. Soc. 2003, 125, 1692-1693.
17. Porter, J. R.; Traverse, J. F.; Hoveyda, A. H.; Snapper, M. L. J. Am. Chem. Soc. 2001, 123, 10409-10410.
18. For a review of Zr-catalyzed asymmetric transformations, see: Hoveyda, A. H. In Titanium and Zirconium in Organic Synthesis; Marek, I., Ed.; VCH-Wiley: Weinheim, 2002; pp 180-229.
19. For a review of asymmetric syntheses of propargylamines, see: Blanchet, J.; Bonin, M.; Micouin, L. Org. Prep. Proced. Int. 2002, 34, 459.
20. Akullian, L. C.; Snapper, M. L.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2003, 42, in press.
21. (a) Wei, C.; Li, C.-J. J. Am. Chem. Soc. 2002, 124, 5638-5639.
22. (b) Koradin, C.; Gommermann, N.; Polborn, K.; Knochel, P. Chem. Eur. J. 2003, 9, 2797-2811.
23. (c) Koradin, C.; Polborn, K.; Knochel, P. Angew. Chem., Int. Ed. 2002, 41, 2535-2538.
24. For enantioselective synthesis of propargylamines through the use of chiral controllers and auxiliaries, see: (d) Huffman, M. A.; Yasuda, N.; DeCamp, A. E.; Grabowski, E. J. J. J. Org. Chem. 1995, 60, 1590-1594. (e) Kolb, M.; Barth, A. Angew. Chem., Int. Ed. Engl. 1980, 19, 725-726. (f) Hattori, K.; Miyata, M.; Yamamoto, H. J. Am. Chem. Soc. 1993, 115, 1151-1152. (g) Enders, D. ; Schankat, J. Helv. Chim. Acta 1995, 78, 970-992. (h) Blanchet, J.; Bonin, M.; Chiaroni, A.; Micouin, L.; Riche, C.; Husson, H.-P. Tetrahedron Lett. 1999, 40, 2935-2938. (i) Fassler, R.; Frantz, D. E.; Oetiker, J.; Carreira, E. M. Angew. Chem., Int. Ed. 2002, 41, 3054-3056. (j) Blanchet, J.; Bonin, M.; Micouin, L.; Husson, H.-P. J. Org. Chem. 2000, 65, 6423-6426. For an example regarding synthesis of optically pure propargylamines through enzymatic resolution, see: (k) Messina, F.; Botta, M.; Corelli, F.; Schneider, M. P.; Fazio, F. J. Org. Chem. 1999, 64, 3767-3769.
25. For enantioselective synthesis of propargylamines through the use of chiral controllers and auxiliaries, see: (d) Huffman, M. A.; Yasuda, N.; DeCamp, A. E.; Grabowski, E. J. J. J. Org. Chem. 1995, 60, 1590-1594. (e) Kolb, M.; Barth, A. Angew. Chem., Int. Ed. Engl. 1980, 19, 725-726. (f) Hattori, K.; Miyata, M.; Yamamoto, H. J. Am. Chem. Soc. 1993, 115, 1151-1152. (g) Enders, D. ; Schankat, J. Helv. Chim. Acta 1995, 78, 970-992. (h) Blanchet, J.; Bonin, M.; Chiaroni, A.; Micouin, L.; Riche, C.; Husson, H.-P. Tetrahedron Lett. 1999, 40, 2935-2938. (i) Fassler, R.; Frantz, D. E.; Oetiker, J.; Carreira, E. M. Angew. Chem., Int. Ed. 2002, 41, 3054-3056. (j) Blanchet, J.; Bonin, M.; Micouin, L.; Husson, H.-P. J. Org. Chem. 2000, 65, 6423-6426. For an example regarding synthesis of optically pure propargylamines through enzymatic resolution, see: (k) Messina, F.; Botta, M.; Corelli, F.; Schneider, M. P.; Fazio, F. J. Org. Chem. 1999, 64, 3767-3769.
26. For enantioselective synthesis of propargylamines through the use of chiral controllers and auxiliaries, see: (d) Huffman, M. A.; Yasuda, N.; DeCamp, A. E.; Grabowski, E. J. J. J. Org. Chem. 1995, 60, 1590-1594. (e) Kolb, M.; Barth, A. Angew. Chem., Int. Ed. Engl. 1980, 19, 725-726. (f) Hattori, K.; Miyata, M.; Yamamoto, H. J. Am. Chem. Soc. 1993, 115, 1151-1152. (g) Enders, D. ; Schankat, J. Helv. Chim. Acta 1995, 78, 970-992. (h) Blanchet, J.; Bonin, M.; Chiaroni, A.; Micouin, L.; Riche, C.; Husson, H.-P. Tetrahedron Lett. 1999, 40, 2935-2938. (i) Fassler, R.; Frantz, D. E.; Oetiker, J.; Carreira, E. M. Angew. Chem., Int. Ed. 2002, 41, 3054-3056. (j) Blanchet, J.; Bonin, M.; Micouin, L.; Husson, H.-P. J. Org. Chem. 2000, 65, 6423-6426. For an example regarding synthesis of optically pure propargylamines through enzymatic resolution, see: (k) Messina, F.; Botta, M.; Corelli, F.; Schneider, M. P.; Fazio, F. J. Org. Chem. 1999, 64, 3767-3769.
27. For enantioselective synthesis of propargylamines through the use of chiral controllers and auxiliaries, see: (d) Huffman, M. A.; Yasuda, N.; DeCamp, A. E.; Grabowski, E. J. J. J. Org. Chem. 1995, 60, 1590-1594. (e) Kolb, M.; Barth, A. Angew. Chem., Int. Ed. Engl. 1980, 19, 725-726. (f) Hattori, K.; Miyata, M.; Yamamoto, H. J. Am. Chem. Soc. 1993, 115, 1151-1152. (g) Enders, D. ; Schankat, J. Helv. Chim. Acta 1995, 78, 970-992. (h) Blanchet, J.; Bonin, M.; Chiaroni, A.; Micouin, L.; Riche, C.; Husson, H.-P. Tetrahedron Lett. 1999, 40, 2935-2938. (i) Fassler, R.; Frantz, D. E.; Oetiker, J.; Carreira, E. M. Angew. Chem., Int. Ed. 2002, 41, 3054-3056. (j) Blanchet, J.; Bonin, M.; Micouin, L.; Husson, H.-P. J. Org. Chem. 2000, 65, 6423-6426. For an example regarding synthesis of optically pure propargylamines through enzymatic resolution, see: (k) Messina, F.; Botta, M.; Corelli, F.; Schneider, M. P.; Fazio, F. J. Org. Chem. 1999, 64, 3767-3769.
28. For enantioselective synthesis of propargylamines through the use of chiral controllers and auxiliaries, see: (d) Huffman, M. A.; Yasuda, N.; DeCamp, A. E.; Grabowski, E. J. J. J. Org. Chem. 1995, 60, 1590-1594. (e) Kolb, M.; Barth, A. Angew. Chem., Int. Ed. Engl. 1980, 19, 725-726. (f) Hattori, K.; Miyata, M.; Yamamoto, H. J. Am. Chem. Soc. 1993, 115, 1151-1152. (g) Enders, D. ; Schankat, J. Helv. Chim. Acta 1995, 78, 970-992. (h) Blanchet, J.; Bonin, M.; Chiaroni, A.; Micouin, L.; Riche, C.; Husson, H.-P. Tetrahedron Lett. 1999, 40, 2935-2938. (i) Fassler, R.; Frantz, D. E.; Oetiker, J.; Carreira, E. M. Angew. Chem., Int. Ed. 2002, 41, 3054-3056. (j) Blanchet, J.; Bonin, M.; Micouin, L.; Husson, H.-P. J. Org. Chem. 2000, 65, 6423-6426. For an example regarding synthesis of optically pure propargylamines through enzymatic resolution, see: (k) Messina, F.; Botta, M.; Corelli, F.; Schneider, M. P.; Fazio, F. J. Org. Chem. 1999, 64, 3767-3769.
29. For enantioselective synthesis of propargylamines through the use of chiral controllers and auxiliaries, see: (d) Huffman, M. A.; Yasuda, N.; DeCamp, A. E.; Grabowski, E. J. J. J. Org. Chem. 1995, 60, 1590-1594. (e) Kolb, M.; Barth, A. Angew. Chem., Int. Ed. Engl. 1980, 19, 725-726. (f) Hattori, K.; Miyata, M.; Yamamoto, H. J. Am. Chem. Soc. 1993, 115, 1151-1152. (g) Enders, D. ; Schankat, J. Helv. Chim. Acta 1995, 78, 970-992. (h) Blanchet, J.; Bonin, M.; Chiaroni, A.; Micouin, L.; Riche, C.; Husson, H.-P. Tetrahedron Lett. 1999, 40, 2935-2938. (i) Fassler, R.; Frantz, D. E.; Oetiker, J.; Carreira, E. M. Angew. Chem., Int. Ed. 2002, 41, 3054-3056. (j) Blanchet, J.; Bonin, M.; Micouin, L.; Husson, H.-P. J. Org. Chem. 2000, 65, 6423-6426. For an example regarding synthesis of optically pure propargylamines through enzymatic resolution, see: (k) Messina, F.; Botta, M.; Corelli, F.; Schneider, M. P.; Fazio, F. J. Org. Chem. 1999, 64, 3767-3769.
30. For enantioselective synthesis of propargylamines through the use of chiral controllers and auxiliaries, see: (d) Huffman, M. A.; Yasuda, N.; DeCamp, A. E.; Grabowski, E. J. J. J. Org. Chem. 1995, 60, 1590-1594. (e) Kolb, M.; Barth, A. Angew. Chem., Int. Ed. Engl. 1980, 19, 725-726. (f) Hattori, K.; Miyata, M.; Yamamoto, H. J. Am. Chem. Soc. 1993, 115, 1151-1152. (g) Enders, D. ; Schankat, J. Helv. Chim. Acta 1995, 78, 970-992. (h) Blanchet, J.; Bonin, M.; Chiaroni, A.; Micouin, L.; Riche, C.; Husson, H.-P. Tetrahedron Lett. 1999, 40, 2935-2938. (i) Fassler, R.; Frantz, D. E.; Oetiker, J.; Carreira, E. M. Angew. Chem., Int. Ed. 2002, 41, 3054-3056. (j) Blanchet, J.; Bonin, M.; Micouin, L.; Husson, H.-P. J. Org. Chem. 2000, 65, 6423-6426. For an example regarding synthesis of optically pure propargylamines through enzymatic resolution, see: (k) Messina, F.; Botta, M.; Corelli, F.; Schneider, M. P.; Fazio, F. J. Org. Chem. 1999, 64, 3767-3769.
31. For enantioselective synthesis of propargylamines through the use of chiral controllers and auxiliaries, see: (d) Huffman, M. A.; Yasuda, N.; DeCamp, A. E.; Grabowski, E. J. J. J. Org. Chem. 1995, 60, 1590-1594. (e) Kolb, M.; Barth, A. Angew. Chem., Int. Ed. Engl. 1980, 19, 725-726. (f) Hattori, K.; Miyata, M.; Yamamoto, H. J. Am. Chem. Soc. 1993, 115, 1151-1152. (g) Enders, D. ; Schankat, J. Helv. Chim. Acta 1995, 78, 970-992. (h) Blanchet, J.; Bonin, M.; Chiaroni, A.; Micouin, L.; Riche, C.; Husson, H.-P. Tetrahedron Lett. 1999, 40, 2935-2938. (i) Fassler, R.; Frantz, D. E.; Oetiker, J.; Carreira, E. M. Angew. Chem., Int. Ed. 2002, 41, 3054-3056. (j) Blanchet, J.; Bonin, M.; Micouin, L.; Husson, H.-P. J. Org. Chem. 2000, 65, 6423-6426. For an example regarding synthesis of optically pure propargylamines through enzymatic resolution, see: (k) Messina, F.; Botta, M.; Corelli, F.; Schneider, M. P.; Fazio, F. J. Org. Chem. 1999, 64, 3767-3769.
32. It is likely that such a lack of reactivity is partly due to the low solubility of dialkynylzinc reagents in toluene. Initial studies indicated that catalytic alkylations in THF, a solvent that more effectively dissolves alkynylzincs, lead to significantly lower enantioselectivity.
33. (a) Berger, S.; Langer, F.; Lutz, C.; Knochel, P.; Mobley, T. A.; Kishan Reddy, C. Angew. Chem., Int. Ed. Engl. 1997, 36, 1496-1498.
34. (b) Bertz, S. H.; Eriksson, M.; Snyder, J. P. J. Am. Chem. Soc. 1996, 118, 10906-10907.
35. See Supporting Information for details.
36. 2Zn resulted in the formation of amines derived from predominant or exclusive addition of a Me group. See: Li, Z.; Upadhyay, V.; DeCamp, A. E.; DiMichele, L.; Reider, P. J. Synthesis 1999, 1453-1458.
37. For representative examples, see: (a) Ritleng, V.; Sirlin, C.; Pfeffer, M. Chem. Rev. 2002, 102, 1731-1769. (b) Negishi, E.; Anastasia, L. Chem. Rev. 2003, 103, 1979-2017.
38. For representative examples, see: (a) Ritleng, V.; Sirlin, C.; Pfeffer, M. Chem. Rev. 2002, 102, 1731-1769. (b) Negishi, E.; Anastasia, L. Chem. Rev. 2003, 103, 1979-2017.
39. Alkynylzincs 1-2 equiv vs 0.6 equiv) derived from 1-hexyne and phenylacetylene are required for efficient Zr-catalyzed alkynylations (see Supporting Information for details). For example, with 0.6 equiv of the alkynylzinc reagent, 6 is obtained in 50-58% yield (vs 81%).
40. For example, see: (a) Shirota, F. N.; DeMaster, E. G.; Nagasawa, H. T. J. Med. Chem. 1979, 22, 463-464. (b) Yu, P. H.; Davis, B. A.; Boulton, A. A. J. Med. Chem. 1992, 35, 3705-3713.
41. For example, see: (a) Shirota, F. N.; DeMaster, E. G.; Nagasawa, H. T. J. Med. Chem. 1979, 22, 463-464. (b) Yu, P. H.; Davis, B. A.; Boulton, A. A. J. Med. Chem. 1992, 35, 3705-3713.