The first catalytic enantioselective Diels-Alder reactions of 1,2-dihydropyridine: Efficient syntheses of optically active 2-azabicyclo[2.2.2]octanes with chiral BINAM derived Cr(III) salen complexes

Tetrahedron

Volumn 58, Issue 41, 2002, Pages 8299-8305

  Takenaka, Norito ^a   Huang, Yong ^a   Rawal, Viresh H ^a  

^a UNIVERSITY OF CHICAGO   (United States)

Author keywords

2 azabicyclo 2.2.2 octane; Alkaloids; Asymmetric catalysis; Diels Alder reaction; Enantioselective

Indexed keywords

1,2 DIHYDROPYRIDINE; 2 AZABICYCLO[2.2.2]OCTANE DERIVATIVE; CHROMIUM DERIVATIVE; DIHYDROPYRIDINE DERIVATIVE; N ACRYLOYLOXAZOLIDINONE; OXAZOLIDINONE DERIVATIVE; SCHIFF BASE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CATALYST; CYCLOADDITION; DIASTEREOISOMER; DIELS ALDER REACTION; DRUG SYNTHESIS; ENANTIOSELECTIVITY; NUCLEAR MAGNETIC RESONANCE; PRIORITY JOURNAL;

BETULACEAE;

EID: 0037037936     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(02)00980-8     Document Type: Article

References (65)

1. Total syntheses of Iboga alkaloids via the Diels-Alder reaction of a dihydropyridine with a dienophile. (±)-Ibogamine: (a) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 87:1965;2073-2075 (b) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 88:1966;3099-3109 (c) Ikezaki M., Wakamatsu T., Ban Y. J. Chem. Soc., Chem. Commun. 1969;88-89. (±)-Catharanthine (d) Büchi G., Kulsa P., Ogasawara K., Rosati R.L. J. Am. Chem. Soc. 92:1970;999-1005 (e) Marazano C., LeGoff M., Fourrey J., Das B.C. J. Chem. Soc., Chem. Commun. 1981;389-391 (f) Raucher S., Bray B.L. J. Org. Chem. 50:1985;3236-3237 (g) Kuehne M.E., Bornmann W.G., Earley W.G., Marko I. J. Org. Chem. 51:1986;2913-2927 (h) Raucher S., Bray B.L., Lawrence R.F. J. Am. Chem. Soc. 109:1987;442-446 (i) Reding M.T., Fukuyama T. Org. Lett. 1:1999;973-976. Synthesis of (+)-catharanthine via resolution: (j) Szántay C., Bölcskei H., Gács-Baitz E. Tetrahedron. 46:1990;1711-1732. and references cited therein.
2. Total syntheses of Iboga alkaloids via the Diels-Alder reaction of a dihydropyridine with a dienophile. (±)-Ibogamine: (a) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 87:1965;2073-2075 (b) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 88:1966;3099-3109 (c) Ikezaki M., Wakamatsu T., Ban Y. J. Chem. Soc., Chem. Commun. 1969;88-89. (±)-Catharanthine (d) Büchi G., Kulsa P., Ogasawara K., Rosati R.L. J. Am. Chem. Soc. 92:1970;999-1005 (e) Marazano C., LeGoff M., Fourrey J., Das B.C. J. Chem. Soc., Chem. Commun. 1981;389-391 (f) Raucher S., Bray B.L. J. Org. Chem. 50:1985;3236-3237 (g) Kuehne M.E., Bornmann W.G., Earley W.G., Marko I. J. Org. Chem. 51:1986;2913-2927 (h) Raucher S., Bray B.L., Lawrence R.F. J. Am. Chem. Soc. 109:1987;442-446 (i) Reding M.T., Fukuyama T. Org. Lett. 1:1999;973-976. Synthesis of (+)-catharanthine via resolution: (j) Szántay C., Bölcskei H., Gács-Baitz E. Tetrahedron. 46:1990;1711-1732. and references cited therein.
3. Total syntheses of Iboga alkaloids via the Diels-Alder reaction of a dihydropyridine with a dienophile. (±)-Ibogamine: (a) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 87:1965;2073-2075 (b) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 88:1966;3099-3109 (c) Ikezaki M., Wakamatsu T., Ban Y. J. Chem. Soc., Chem. Commun. 1969;88-89. (±)-Catharanthine (d) Büchi G., Kulsa P., Ogasawara K., Rosati R.L. J. Am. Chem. Soc. 92:1970;999-1005 (e) Marazano C., LeGoff M., Fourrey J., Das B.C. J. Chem. Soc., Chem. Commun. 1981;389-391 (f) Raucher S., Bray B.L. J. Org. Chem. 50:1985;3236-3237 (g) Kuehne M.E., Bornmann W.G., Earley W.G., Marko I. J. Org. Chem. 51:1986;2913-2927 (h) Raucher S., Bray B.L., Lawrence R.F. J. Am. Chem. Soc. 109:1987;442-446 (i) Reding M.T., Fukuyama T. Org. Lett. 1:1999;973-976. Synthesis of (+)-catharanthine via resolution: (j) Szántay C., Bölcskei H., Gács-Baitz E. Tetrahedron. 46:1990;1711-1732. and references cited therein.
4. Total syntheses of Iboga alkaloids via the Diels-Alder reaction of a dihydropyridine with a dienophile. (±)-Ibogamine: (a) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 87:1965;2073-2075 (b) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 88:1966;3099-3109 (c) Ikezaki M., Wakamatsu T., Ban Y. J. Chem. Soc., Chem. Commun. 1969;88-89. (±)-Catharanthine (d) Büchi G., Kulsa P., Ogasawara K., Rosati R.L. J. Am. Chem. Soc. 92:1970;999-1005 (e) Marazano C., LeGoff M., Fourrey J., Das B.C. J. Chem. Soc., Chem. Commun. 1981;389-391 (f) Raucher S., Bray B.L. J. Org. Chem. 50:1985;3236-3237 (g) Kuehne M.E., Bornmann W.G., Earley W.G., Marko I. J. Org. Chem. 51:1986;2913-2927 (h) Raucher S., Bray B.L., Lawrence R.F. J. Am. Chem. Soc. 109:1987;442-446 (i) Reding M.T., Fukuyama T. Org. Lett. 1:1999;973-976. Synthesis of (+)-catharanthine via resolution: (j) Szántay C., Bölcskei H., Gács-Baitz E. Tetrahedron. 46:1990;1711-1732. and references cited therein.
5. Total syntheses of Iboga alkaloids via the Diels-Alder reaction of a dihydropyridine with a dienophile. (±)-Ibogamine: (a) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 87:1965;2073-2075 (b) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 88:1966;3099-3109 (c) Ikezaki M., Wakamatsu T., Ban Y. J. Chem. Soc., Chem. Commun. 1969;88-89. (±)-Catharanthine (d) Büchi G., Kulsa P., Ogasawara K., Rosati R.L. J. Am. Chem. Soc. 92:1970;999-1005 (e) Marazano C., LeGoff M., Fourrey J., Das B.C. J. Chem. Soc., Chem. Commun. 1981;389-391 (f) Raucher S., Bray B.L. J. Org. Chem. 50:1985;3236-3237 (g) Kuehne M.E., Bornmann W.G., Earley W.G., Marko I. J. Org. Chem. 51:1986;2913-2927 (h) Raucher S., Bray B.L., Lawrence R.F. J. Am. Chem. Soc. 109:1987;442-446 (i) Reding M.T., Fukuyama T. Org. Lett. 1:1999;973-976. Synthesis of (+)-catharanthine via resolution: (j) Szántay C., Bölcskei H., Gács-Baitz E. Tetrahedron. 46:1990;1711-1732. and references cited therein.
6. Total syntheses of Iboga alkaloids via the Diels-Alder reaction of a dihydropyridine with a dienophile. (±)-Ibogamine: (a) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 87:1965;2073-2075 (b) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 88:1966;3099-3109 (c) Ikezaki M., Wakamatsu T., Ban Y. J. Chem. Soc., Chem. Commun. 1969;88-89. (±)-Catharanthine (d) Büchi G., Kulsa P., Ogasawara K., Rosati R.L. J. Am. Chem. Soc. 92:1970;999-1005 (e) Marazano C., LeGoff M., Fourrey J., Das B.C. J. Chem. Soc., Chem. Commun. 1981;389-391 (f) Raucher S., Bray B.L. J. Org. Chem. 50:1985;3236-3237 (g) Kuehne M.E., Bornmann W.G., Earley W.G., Marko I. J. Org. Chem. 51:1986;2913-2927 (h) Raucher S., Bray B.L., Lawrence R.F. J. Am. Chem. Soc. 109:1987;442-446 (i) Reding M.T., Fukuyama T. Org. Lett. 1:1999;973-976. Synthesis of (+)-catharanthine via resolution: (j) Szántay C., Bölcskei H., Gács-Baitz E. Tetrahedron. 46:1990;1711-1732. and references cited therein.
7. Total syntheses of Iboga alkaloids via the Diels-Alder reaction of a dihydropyridine with a dienophile. (±)-Ibogamine: (a) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 87:1965;2073-2075 (b) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 88:1966;3099-3109 (c) Ikezaki M., Wakamatsu T., Ban Y. J. Chem. Soc., Chem. Commun. 1969;88-89. (±)-Catharanthine (d) Büchi G., Kulsa P., Ogasawara K., Rosati R.L. J. Am. Chem. Soc. 92:1970;999-1005 (e) Marazano C., LeGoff M., Fourrey J., Das B.C. J. Chem. Soc., Chem. Commun. 1981;389-391 (f) Raucher S., Bray B.L. J. Org. Chem. 50:1985;3236-3237 (g) Kuehne M.E., Bornmann W.G., Earley W.G., Marko I. J. Org. Chem. 51:1986;2913-2927 (h) Raucher S., Bray B.L., Lawrence R.F. J. Am. Chem. Soc. 109:1987;442-446 (i) Reding M.T., Fukuyama T. Org. Lett. 1:1999;973-976. Synthesis of (+)-catharanthine via resolution: (j) Szántay C., Bölcskei H., Gács-Baitz E. Tetrahedron. 46:1990;1711-1732. and references cited therein.
8. Total syntheses of Iboga alkaloids via the Diels-Alder reaction of a dihydropyridine with a dienophile. (±)-Ibogamine: (a) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 87:1965;2073-2075 (b) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 88:1966;3099-3109 (c) Ikezaki M., Wakamatsu T., Ban Y. J. Chem. Soc., Chem. Commun. 1969;88-89. (±)-Catharanthine (d) Büchi G., Kulsa P., Ogasawara K., Rosati R.L. J. Am. Chem. Soc. 92:1970;999-1005 (e) Marazano C., LeGoff M., Fourrey J., Das B.C. J. Chem. Soc., Chem. Commun. 1981;389-391 (f) Raucher S., Bray B.L. J. Org. Chem. 50:1985;3236-3237 (g) Kuehne M.E., Bornmann W.G., Earley W.G., Marko I. J. Org. Chem. 51:1986;2913-2927 (h) Raucher S., Bray B.L., Lawrence R.F. J. Am. Chem. Soc. 109:1987;442-446 (i) Reding M.T., Fukuyama T. Org. Lett. 1:1999;973-976. Synthesis of (+)-catharanthine via resolution: (j) Szántay C., Bölcskei H., Gács-Baitz E. Tetrahedron. 46:1990;1711-1732. and references cited therein.
9. Total syntheses of Iboga alkaloids via the Diels-Alder reaction of a dihydropyridine with a dienophile. (±)-Ibogamine: (a) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 87:1965;2073-2075 (b) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 88:1966;3099-3109 (c) Ikezaki M., Wakamatsu T., Ban Y. J. Chem. Soc., Chem. Commun. 1969;88-89. (±)-Catharanthine (d) Büchi G., Kulsa P., Ogasawara K., Rosati R.L. J. Am. Chem. Soc. 92:1970;999-1005 (e) Marazano C., LeGoff M., Fourrey J., Das B.C. J. Chem. Soc., Chem. Commun. 1981;389-391 (f) Raucher S., Bray B.L. J. Org. Chem. 50:1985;3236-3237 (g) Kuehne M.E., Bornmann W.G., Earley W.G., Marko I. J. Org. Chem. 51:1986;2913-2927 (h) Raucher S., Bray B.L., Lawrence R.F. J. Am. Chem. Soc. 109:1987;442-446 (i) Reding M.T., Fukuyama T. Org. Lett. 1:1999;973-976. Synthesis of (+)-catharanthine via resolution: (j) Szántay C., Bölcskei H., Gács-Baitz E. Tetrahedron. 46:1990;1711-1732. and references cited therein.
10. Total syntheses of Iboga alkaloids via the Diels-Alder reaction of a dihydropyridine with a dienophile. (±)-Ibogamine: (a) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 87:1965;2073-2075 (b) Büchi G., Coffen D.L., Kocsis K., Sonnet P.E., Ziegler F.E. J. Am. Chem. Soc. 88:1966;3099-3109 (c) Ikezaki M., Wakamatsu T., Ban Y. J. Chem. Soc., Chem. Commun. 1969;88-89. (±)-Catharanthine (d) Büchi G., Kulsa P., Ogasawara K., Rosati R.L. J. Am. Chem. Soc. 92:1970;999-1005 (e) Marazano C., LeGoff M., Fourrey J., Das B.C. J. Chem. Soc., Chem. Commun. 1981;389-391 (f) Raucher S., Bray B.L. J. Org. Chem. 50:1985;3236-3237 (g) Kuehne M.E., Bornmann W.G., Earley W.G., Marko I. J. Org. Chem. 51:1986;2913-2927 (h) Raucher S., Bray B.L., Lawrence R.F. J. Am. Chem. Soc. 109:1987;442-446 (i) Reding M.T., Fukuyama T. Org. Lett. 1:1999;973-976. Synthesis of (+)-catharanthine via resolution: (j) Szántay C., Bölcskei H., Gács-Baitz E. Tetrahedron. 46:1990;1711-1732. and references cited therein.
11. (a) Kuehne M.E., Markó I. Brossi A., Suffness M., The Alkaloids. Antitumor Bisindole Alkaloids from Catharanthus roseus (L.). The Alkaloids. Antitumor Bisindole Alkaloids from Catharanthus roseus (L.). Vol. 37:1990;77-131 Academic, San Diego,
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13. (a) Brossi A., Suffness M., The Alkaloids. Antitumor Bisindole Alkaloids from Catharanthus roseus (L.). Vol. 37:1990;Academic, San Diego,
14. (b) Popik P., Skolnick P. Cordell G.A., The Alkaloids. Chemistry and Biology. The Alkaloids. Chemistry and Biology. Vol. 52:1999;197-231 Academic, San Diego,
15. (c) Glick S.D., Maisonneuve I.M., Szumlinski K.K. Alper K.R., Glick S.D., Cordell G.A., The Alkaloids. The Alkaloids. Vol. 56:2001;39-53 Academic, San Diego.
16. For our work on the synthesis of the Aspidosperma portion, see: (a) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 120:1998;13523-13524 (b) Kozmin S.A., Iwama T., Huang Y., Rawal V.H. J. Am. Chem. Soc. 124:2002;4628-4641. For other papers on the chemistry of amino siloxy dienes, see: (c) Kozmin S.A., Rawal V.H. J. Org. Chem. 62:1997;5252-5253 (d) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 119:1997;7165-7166 (e) Kozmin S.A., Janey J.M., Rawal V.H. J. Org. Chem. 64:1999;3039-3052 (f) Kozmin S.A., Green M.T., Rawal V.H. J. Org. Chem. 64:1999;8045-8047 (g) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 121:1999;9562-9573 (h) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;152 (i) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;160 (j) Janey J.M., Iwama T., Kozmin S.A., Rawal V.H. J. Org. Chem. 65:2000;9059-9068 (k) Huang Y., Rawal V.H. Org. Lett. 2:2000;3321-3323.
17. For our work on the synthesis of the Aspidosperma portion, see: (a) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 120:1998;13523-13524 (b) Kozmin S.A., Iwama T., Huang Y., Rawal V.H. J. Am. Chem. Soc. 124:2002;4628-4641. For other papers on the chemistry of amino siloxy dienes, see: (c) Kozmin S.A., Rawal V.H. J. Org. Chem. 62:1997;5252-5253 (d) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 119:1997;7165-7166 (e) Kozmin S.A., Janey J.M., Rawal V.H. J. Org. Chem. 64:1999;3039-3052 (f) Kozmin S.A., Green M.T., Rawal V.H. J. Org. Chem. 64:1999;8045-8047 (g) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 121:1999;9562-9573 (h) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;152 (i) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;160 (j) Janey J.M., Iwama T., Kozmin S.A., Rawal V.H. J. Org. Chem. 65:2000;9059-9068 (k) Huang Y., Rawal V.H. Org. Lett. 2:2000;3321-3323.
18. For our work on the synthesis of the Aspidosperma portion, see: (a) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 120:1998;13523-13524 (b) Kozmin S.A., Iwama T., Huang Y., Rawal V.H. J. Am. Chem. Soc. 124:2002;4628-4641. For other papers on the chemistry of amino siloxy dienes, see: (c) Kozmin S.A., Rawal V.H. J. Org. Chem. 62:1997;5252-5253 (d) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 119:1997;7165-7166 (e) Kozmin S.A., Janey J.M., Rawal V.H. J. Org. Chem. 64:1999;3039-3052 (f) Kozmin S.A., Green M.T., Rawal V.H. J. Org. Chem. 64:1999;8045-8047 (g) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 121:1999;9562-9573 (h) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;152 (i) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;160 (j) Janey J.M., Iwama T., Kozmin S.A., Rawal V.H. J. Org. Chem. 65:2000;9059-9068 (k) Huang Y., Rawal V.H. Org. Lett. 2:2000;3321-3323.
19. For our work on the synthesis of the Aspidosperma portion, see: (a) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 120:1998;13523-13524 (b) Kozmin S.A., Iwama T., Huang Y., Rawal V.H. J. Am. Chem. Soc. 124:2002;4628-4641. For other papers on the chemistry of amino siloxy dienes, see: (c) Kozmin S.A., Rawal V.H. J. Org. Chem. 62:1997;5252-5253 (d) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 119:1997;7165-7166 (e) Kozmin S.A., Janey J.M., Rawal V.H. J. Org. Chem. 64:1999;3039-3052 (f) Kozmin S.A., Green M.T., Rawal V.H. J. Org. Chem. 64:1999;8045-8047 (g) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 121:1999;9562-9573 (h) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;152 (i) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;160 (j) Janey J.M., Iwama T., Kozmin S.A., Rawal V.H. J. Org. Chem. 65:2000;9059-9068 (k) Huang Y., Rawal V.H. Org. Lett. 2:2000;3321-3323.
20. For our work on the synthesis of the Aspidosperma portion, see: (a) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 120:1998;13523-13524 (b) Kozmin S.A., Iwama T., Huang Y., Rawal V.H. J. Am. Chem. Soc. 124:2002;4628-4641. For other papers on the chemistry of amino siloxy dienes, see: (c) Kozmin S.A., Rawal V.H. J. Org. Chem. 62:1997;5252-5253 (d) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 119:1997;7165-7166 (e) Kozmin S.A., Janey J.M., Rawal V.H. J. Org. Chem. 64:1999;3039-3052 (f) Kozmin S.A., Green M.T., Rawal V.H. J. Org. Chem. 64:1999;8045-8047 (g) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 121:1999;9562-9573 (h) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;152 (i) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;160 (j) Janey J.M., Iwama T., Kozmin S.A., Rawal V.H. J. Org. Chem. 65:2000;9059-9068 (k) Huang Y., Rawal V.H. Org. Lett. 2:2000;3321-3323.
21. For our work on the synthesis of the Aspidosperma portion, see: (a) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 120:1998;13523-13524 (b) Kozmin S.A., Iwama T., Huang Y., Rawal V.H. J. Am. Chem. Soc. 124:2002;4628-4641. For other papers on the chemistry of amino siloxy dienes, see: (c) Kozmin S.A., Rawal V.H. J. Org. Chem. 62:1997;5252-5253 (d) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 119:1997;7165-7166 (e) Kozmin S.A., Janey J.M., Rawal V.H. J. Org. Chem. 64:1999;3039-3052 (f) Kozmin S.A., Green M.T., Rawal V.H. J. Org. Chem. 64:1999;8045-8047 (g) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 121:1999;9562-9573 (h) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;152 (i) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;160 (j) Janey J.M., Iwama T., Kozmin S.A., Rawal V.H. J. Org. Chem. 65:2000;9059-9068 (k) Huang Y., Rawal V.H. Org. Lett. 2:2000;3321-3323.
22. For our work on the synthesis of the Aspidosperma portion, see: (a) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 120:1998;13523-13524 (b) Kozmin S.A., Iwama T., Huang Y., Rawal V.H. J. Am. Chem. Soc. 124:2002;4628-4641. For other papers on the chemistry of amino siloxy dienes, see: (c) Kozmin S.A., Rawal V.H. J. Org. Chem. 62:1997;5252-5253 (d) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 119:1997;7165-7166 (e) Kozmin S.A., Janey J.M., Rawal V.H. J. Org. Chem. 64:1999;3039-3052 (f) Kozmin S.A., Green M.T., Rawal V.H. J. Org. Chem. 64:1999;8045-8047 (g) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 121:1999;9562-9573 (h) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;152 (i) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;160 (j) Janey J.M., Iwama T., Kozmin S.A., Rawal V.H. J. Org. Chem. 65:2000;9059-9068 (k) Huang Y., Rawal V.H. Org. Lett. 2:2000;3321-3323.
23. For our work on the synthesis of the Aspidosperma portion, see: (a) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 120:1998;13523-13524 (b) Kozmin S.A., Iwama T., Huang Y., Rawal V.H. J. Am. Chem. Soc. 124:2002;4628-4641. For other papers on the chemistry of amino siloxy dienes, see: (c) Kozmin S.A., Rawal V.H. J. Org. Chem. 62:1997;5252-5253 (d) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 119:1997;7165-7166 (e) Kozmin S.A., Janey J.M., Rawal V.H. J. Org. Chem. 64:1999;3039-3052 (f) Kozmin S.A., Green M.T., Rawal V.H. J. Org. Chem. 64:1999;8045-8047 (g) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 121:1999;9562-9573 (h) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;152 (i) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;160 (j) Janey J.M., Iwama T., Kozmin S.A., Rawal V.H. J. Org. Chem. 65:2000;9059-9068 (k) Huang Y., Rawal V.H. Org. Lett. 2:2000;3321-3323.
24. For our work on the synthesis of the Aspidosperma portion, see: (a) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 120:1998;13523-13524 (b) Kozmin S.A., Iwama T., Huang Y., Rawal V.H. J. Am. Chem. Soc. 124:2002;4628-4641. For other papers on the chemistry of amino siloxy dienes, see: (c) Kozmin S.A., Rawal V.H. J. Org. Chem. 62:1997;5252-5253 (d) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 119:1997;7165-7166 (e) Kozmin S.A., Janey J.M., Rawal V.H. J. Org. Chem. 64:1999;3039-3052 (f) Kozmin S.A., Green M.T., Rawal V.H. J. Org. Chem. 64:1999;8045-8047 (g) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 121:1999;9562-9573 (h) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;152 (i) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;160 (j) Janey J.M., Iwama T., Kozmin S.A., Rawal V.H. J. Org. Chem. 65:2000;9059-9068 (k) Huang Y., Rawal V.H. Org. Lett. 2:2000;3321-3323.
25. For our work on the synthesis of the Aspidosperma portion, see: (a) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 120:1998;13523-13524 (b) Kozmin S.A., Iwama T., Huang Y., Rawal V.H. J. Am. Chem. Soc. 124:2002;4628-4641. For other papers on the chemistry of amino siloxy dienes, see: (c) Kozmin S.A., Rawal V.H. J. Org. Chem. 62:1997;5252-5253 (d) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 119:1997;7165-7166 (e) Kozmin S.A., Janey J.M., Rawal V.H. J. Org. Chem. 64:1999;3039-3052 (f) Kozmin S.A., Green M.T., Rawal V.H. J. Org. Chem. 64:1999;8045-8047 (g) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 121:1999;9562-9573 (h) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;152 (i) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;160 (j) Janey J.M., Iwama T., Kozmin S.A., Rawal V.H. J. Org. Chem. 65:2000;9059-9068 (k) Huang Y., Rawal V.H. Org. Lett. 2:2000;3321-3323.
26. For our work on the synthesis of the Aspidosperma portion, see: (a) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 120:1998;13523-13524 (b) Kozmin S.A., Iwama T., Huang Y., Rawal V.H. J. Am. Chem. Soc. 124:2002;4628-4641. For other papers on the chemistry of amino siloxy dienes, see: (c) Kozmin S.A., Rawal V.H. J. Org. Chem. 62:1997;5252-5253 (d) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 119:1997;7165-7166 (e) Kozmin S.A., Janey J.M., Rawal V.H. J. Org. Chem. 64:1999;3039-3052 (f) Kozmin S.A., Green M.T., Rawal V.H. J. Org. Chem. 64:1999;8045-8047 (g) Kozmin S.A., Rawal V.H. J. Am. Chem. Soc. 121:1999;9562-9573 (h) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;152 (i) Kozmin S.A., He S., Rawal V.H. Org. Synth. 78:2000;160 (j) Janey J.M., Iwama T., Kozmin S.A., Rawal V.H. J. Org. Chem. 65:2000;9059-9068 (k) Huang Y., Rawal V.H. Org. Lett. 2:2000;3321-3323.
27. For 1,2-dihydropyridine possessing a chiral centre: (a) Matsumura Y., Nakamura Y., Maki T., Onomura O. Tetrahedron Lett. 41:2000;7685-7689. Dihydropyridine having a chiral auxiliary attached to the nitrogen: (b) Mehmandoust M., Marazano C., Singh R., Gillet B., Césario M., Fourrey J.-L., Das B.C. Tetrahedron Lett. 29:1988;4423-4426 (c) Marazano C., Yannic Y., Mehmandoust M., Das B.C. Tetrahedron Lett. 31:1990;1995-1998. Diels-Alder reactions in which the dienophile has a chiral auxiliary: (d) Kouklovsky C., Pouilhès A., Langlois Y. J. Am. Chem. Soc. 112:1990;6672-6679 (e) Campbell M.M., Sainsbury M., Searle P.A., Davis G.M. Tetrahedron Lett. 33:1992;3181-3184. Selected leading references on the racemic Diels-Alder reaction of dihydropyridines: (f) Craig D., Kuder A.K., Efroymson J. J. Am. Chem. Soc. 72:1950;5236-5238 (g) Sliwa H., Bot Y.L. Tetrahedron Lett. 18:1977;4129-4132 (h) Campbell M.M., Mahon M.F., Sainsbury M., Searle P.A., Davies G.M. Tetrahedron Lett. 32:1991;951-954.
28. For 1,2-dihydropyridine possessing a chiral centre: (a) Matsumura Y., Nakamura Y., Maki T., Onomura O. Tetrahedron Lett. 41:2000;7685-7689. Dihydropyridine having a chiral auxiliary attached to the nitrogen: (b) Mehmandoust M., Marazano C., Singh R., Gillet B., Césario M., Fourrey J.-L., Das B.C. Tetrahedron Lett. 29:1988;4423-4426 (c) Marazano C., Yannic Y., Mehmandoust M., Das B.C. Tetrahedron Lett. 31:1990;1995-1998. Diels-Alder reactions in which the dienophile has a chiral auxiliary: (d) Kouklovsky C., Pouilhès A., Langlois Y. J. Am. Chem. Soc. 112:1990;6672-6679 (e) Campbell M.M., Sainsbury M., Searle P.A., Davis G.M. Tetrahedron Lett. 33:1992;3181-3184. Selected leading references on the racemic Diels-Alder reaction of dihydropyridines: (f) Craig D., Kuder A.K., Efroymson J. J. Am. Chem. Soc. 72:1950;5236-5238 (g) Sliwa H., Bot Y.L. Tetrahedron Lett. 18:1977;4129-4132 (h) Campbell M.M., Mahon M.F., Sainsbury M., Searle P.A., Davies G.M. Tetrahedron Lett. 32:1991;951-954.
29. For 1,2-dihydropyridine possessing a chiral centre: (a) Matsumura Y., Nakamura Y., Maki T., Onomura O. Tetrahedron Lett. 41:2000;7685-7689. Dihydropyridine having a chiral auxiliary attached to the nitrogen: (b) Mehmandoust M., Marazano C., Singh R., Gillet B., Césario M., Fourrey J.-L., Das B.C. Tetrahedron Lett. 29:1988;4423-4426 (c) Marazano C., Yannic Y., Mehmandoust M., Das B.C. Tetrahedron Lett. 31:1990;1995-1998. Diels-Alder reactions in which the dienophile has a chiral auxiliary: (d) Kouklovsky C., Pouilhès A., Langlois Y. J. Am. Chem. Soc. 112:1990;6672-6679 (e) Campbell M.M., Sainsbury M., Searle P.A., Davis G.M. Tetrahedron Lett. 33:1992;3181-3184. Selected leading references on the racemic Diels-Alder reaction of dihydropyridines: (f) Craig D., Kuder A.K., Efroymson J. J. Am. Chem. Soc. 72:1950;5236-5238 (g) Sliwa H., Bot Y.L. Tetrahedron Lett. 18:1977;4129-4132 (h) Campbell M.M., Mahon M.F., Sainsbury M., Searle P.A., Davies G.M. Tetrahedron Lett. 32:1991;951-954.
30. For 1,2-dihydropyridine possessing a chiral centre: (a) Matsumura Y., Nakamura Y., Maki T., Onomura O. Tetrahedron Lett. 41:2000;7685-7689. Dihydropyridine having a chiral auxiliary attached to the nitrogen: (b) Mehmandoust M., Marazano C., Singh R., Gillet B., Césario M., Fourrey J.-L., Das B.C. Tetrahedron Lett. 29:1988;4423-4426 (c) Marazano C., Yannic Y., Mehmandoust M., Das B.C. Tetrahedron Lett. 31:1990;1995-1998. Diels-Alder reactions in which the dienophile has a chiral auxiliary: (d) Kouklovsky C., Pouilhès A., Langlois Y. J. Am. Chem. Soc. 112:1990;6672-6679 (e) Campbell M.M., Sainsbury M., Searle P.A., Davis G.M. Tetrahedron Lett. 33:1992;3181-3184. Selected leading references on the racemic Diels-Alder reaction of dihydropyridines: (f) Craig D., Kuder A.K., Efroymson J. J. Am. Chem. Soc. 72:1950;5236-5238 (g) Sliwa H., Bot Y.L. Tetrahedron Lett. 18:1977;4129-4132 (h) Campbell M.M., Mahon M.F., Sainsbury M., Searle P.A., Davies G.M. Tetrahedron Lett. 32:1991;951-954.
31. For 1,2-dihydropyridine possessing a chiral centre: (a) Matsumura Y., Nakamura Y., Maki T., Onomura O. Tetrahedron Lett. 41:2000;7685-7689. Dihydropyridine having a chiral auxiliary attached to the nitrogen: (b) Mehmandoust M., Marazano C., Singh R., Gillet B., Césario M., Fourrey J.-L., Das B.C. Tetrahedron Lett. 29:1988;4423-4426 (c) Marazano C., Yannic Y., Mehmandoust M., Das B.C. Tetrahedron Lett. 31:1990;1995-1998. Diels-Alder reactions in which the dienophile has a chiral auxiliary: (d) Kouklovsky C., Pouilhès A., Langlois Y. J. Am. Chem. Soc. 112:1990;6672-6679 (e) Campbell M.M., Sainsbury M., Searle P.A., Davis G.M. Tetrahedron Lett. 33:1992;3181-3184. Selected leading references on the racemic Diels-Alder reaction of dihydropyridines: (f) Craig D., Kuder A.K., Efroymson J. J. Am. Chem. Soc. 72:1950;5236-5238 (g) Sliwa H., Bot Y.L. Tetrahedron Lett. 18:1977;4129-4132 (h) Campbell M.M., Mahon M.F., Sainsbury M., Searle P.A., Davies G.M. Tetrahedron Lett. 32:1991;951-954.
32. For 1,2-dihydropyridine possessing a chiral centre: (a) Matsumura Y., Nakamura Y., Maki T., Onomura O. Tetrahedron Lett. 41:2000;7685-7689. Dihydropyridine having a chiral auxiliary attached to the nitrogen: (b) Mehmandoust M., Marazano C., Singh R., Gillet B., Césario M., Fourrey J.-L., Das B.C. Tetrahedron Lett. 29:1988;4423-4426 (c) Marazano C., Yannic Y., Mehmandoust M., Das B.C. Tetrahedron Lett. 31:1990;1995-1998. Diels-Alder reactions in which the dienophile has a chiral auxiliary: (d) Kouklovsky C., Pouilhès A., Langlois Y. J. Am. Chem. Soc. 112:1990;6672-6679 (e) Campbell M.M., Sainsbury M., Searle P.A., Davis G.M. Tetrahedron Lett. 33:1992;3181-3184. Selected leading references on the racemic Diels-Alder reaction of dihydropyridines: (f) Craig D., Kuder A.K., Efroymson J. J. Am. Chem. Soc. 72:1950;5236-5238 (g) Sliwa H., Bot Y.L. Tetrahedron Lett. 18:1977;4129-4132 (h) Campbell M.M., Mahon M.F., Sainsbury M., Searle P.A., Davies G.M. Tetrahedron Lett. 32:1991;951-954.
33. For 1,2-dihydropyridine possessing a chiral centre: (a) Matsumura Y., Nakamura Y., Maki T., Onomura O. Tetrahedron Lett. 41:2000;7685-7689. Dihydropyridine having a chiral auxiliary attached to the nitrogen: (b) Mehmandoust M., Marazano C., Singh R., Gillet B., Césario M., Fourrey J.-L., Das B.C. Tetrahedron Lett. 29:1988;4423-4426 (c) Marazano C., Yannic Y., Mehmandoust M., Das B.C. Tetrahedron Lett. 31:1990;1995-1998. Diels-Alder reactions in which the dienophile has a chiral auxiliary: (d) Kouklovsky C., Pouilhès A., Langlois Y. J. Am. Chem. Soc. 112:1990;6672-6679 (e) Campbell M.M., Sainsbury M., Searle P.A., Davis G.M. Tetrahedron Lett. 33:1992;3181-3184. Selected leading references on the racemic Diels-Alder reaction of dihydropyridines: (f) Craig D., Kuder A.K., Efroymson J. J. Am. Chem. Soc. 72:1950;5236-5238 (g) Sliwa H., Bot Y.L. Tetrahedron Lett. 18:1977;4129-4132 (h) Campbell M.M., Mahon M.F., Sainsbury M., Searle P.A., Davies G.M. Tetrahedron Lett. 32:1991;951-954.
34. For 1,2-dihydropyridine possessing a chiral centre: (a) Matsumura Y., Nakamura Y., Maki T., Onomura O. Tetrahedron Lett. 41:2000;7685-7689. Dihydropyridine having a chiral auxiliary attached to the nitrogen: (b) Mehmandoust M., Marazano C., Singh R., Gillet B., Césario M., Fourrey J.-L., Das B.C. Tetrahedron Lett. 29:1988;4423-4426 (c) Marazano C., Yannic Y., Mehmandoust M., Das B.C. Tetrahedron Lett. 31:1990;1995-1998. Diels-Alder reactions in which the dienophile has a chiral auxiliary: (d) Kouklovsky C., Pouilhès A., Langlois Y. J. Am. Chem. Soc. 112:1990;6672-6679 (e) Campbell M.M., Sainsbury M., Searle P.A., Davis G.M. Tetrahedron Lett. 33:1992;3181-3184. Selected leading references on the racemic Diels-Alder reaction of dihydropyridines: (f) Craig D., Kuder A.K., Efroymson J. J. Am. Chem. Soc. 72:1950;5236-5238 (g) Sliwa H., Bot Y.L. Tetrahedron Lett. 18:1977;4129-4132 (h) Campbell M.M., Mahon M.F., Sainsbury M., Searle P.A., Davies G.M. Tetrahedron Lett. 32:1991;951-954.
35. For a discussion of the biosynthesis of Iboga alkaloids, see: (a) Scott A.I. Acc. Chem. Res. 3:1970;151-157 (b) Atta-Ur-Rahman B.A. Biosynthesis of Indole Alkaloids. 1983;Clarendon, Oxford.
36. For a discussion of the biosynthesis of Iboga alkaloids, see: (a) Scott A.I. Acc. Chem. Res. 3:1970;151-157 (b) Atta-Ur-Rahman B.A. Biosynthesis of Indole Alkaloids. 1983;Clarendon, Oxford.
37. To the best of our knowledge, in the only example of a Lewis acid catalysed Diels-Alder reaction of a 1,2-dihydropyridine, a full equivalent of the Lewis acid was required. See Ref. 5a.
38. For our earlier work on asymmetric catalysis of Diels-Alder reactions of amino dienes, see: (a) Huang Y., Iwama T., Rawal V.H. J. Am. Chem. Soc. 122:2000;7843-7844 (b) Huang Y., Iwama T., Rawal V.H. Org. Lett. 4:2002;1163-1166 (c) Huang Y., Iwama T., Rawal V.H. J. Am. Chem. Soc. 2002;. in press.
39. For our earlier work on asymmetric catalysis of Diels-Alder reactions of amino dienes, see: (a) Huang Y., Iwama T., Rawal V.H. J. Am. Chem. Soc. 122:2000;7843-7844 (b) Huang Y., Iwama T., Rawal V.H. Org. Lett. 4:2002;1163-1166 (c) Huang Y., Iwama T., Rawal V.H. J. Am. Chem. Soc. 2002;. in press.
40. For our earlier work on asymmetric catalysis of Diels-Alder reactions of amino dienes, see: (a) Huang Y., Iwama T., Rawal V.H. J. Am. Chem. Soc. 122:2000;7843-7844 (b) Huang Y., Iwama T., Rawal V.H. Org. Lett. 4:2002;1163-1166 (c) Huang Y., Iwama T., Rawal V.H. J. Am. Chem. Soc. 2002;. in press.
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