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Volumn 46, Issue 29, 2007, Pages 5488-5508

Total synthesis of complex cyclotryptamine alkaloids: Stereocontrolled construction of quaternary carbon stereocenters

Author keywords

Alkaloids; Alkylation; Asymmetric catalysis; Synthetic methods; Total synthesis

Indexed keywords

ALKYLATION; MOLECULAR STRUCTURE; STEREOCHEMISTRY; SYNTHESIS (CHEMICAL);

EID: 34547166889     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200700612     Document Type: Review
Times cited : (405)

References (152)
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    • A halogenated and oxidized version of another such structural isomer of chimonanthine and calycanthine, perophoramidine, has also been isolated: S. M. Verbitski, C. L. Mayne, R. A. Davis, G. P. Concepcion, C. M. Ireland, J. Org. Chem. 2002, 67, 7124-7126
    • A halogenated and oxidized version of another such structural isomer of chimonanthine and calycanthine, perophoramidine, has also been isolated: S. M. Verbitski, C. L. Mayne, R. A. Davis, G. P. Concepcion, C. M. Ireland, J. Org. Chem. 2002, 67, 7124-7126.
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    • Cyclotryptophans have been shown to suffer oxidation at the 3a-position under free radical conditions: M. Bruncko, D. Crich, R. Samy, Heterocycles 1993, 36, 1735-1738.
    • Cyclotryptophans have been shown to suffer oxidation at the 3a-position under free radical conditions: M. Bruncko, D. Crich, R. Samy, Heterocycles 1993, 36, 1735-1738.
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    • The formidable challenge of assembling vicinal stereogenic quaternary stereocenters was discussed in a recent review, see: a E. A. Peterson, L. E. Overman, Proc. Natl. Acad. Sci. USA 2004, 101, 11943-11948;
    • The formidable challenge of assembling vicinal stereogenic quaternary stereocenters was discussed in a recent review, see: a) E. A. Peterson, L. E. Overman, Proc. Natl. Acad. Sci. USA 2004, 101, 11943-11948;
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    • for additional one-step methods not covered in this survey, see: b
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    • Early syntheses of chimonanthine and folicanthine are discussed in several reviews, see: a, Ed, J. ApSimon, Wiley, New York
    • Early syntheses of chimonanthine and folicanthine are discussed in several reviews, see: a) J. P. Kutney in The Total Synthesis of Natural Products, Vol. 3 (Ed.: J. ApSimon), Wiley, New York, 1977, pp. 273-438;
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    • Other means of assembling vicinal quaternary carbon centers, based on radical-radical couplings, have been disclosed: a K. M. Depew, S. P. Marsden, D. Zatorska, A. Zatorski, W. G. Bornmann, S. J. Danishefsky, J. Am. Chem. Soc. 1999, 121, 11953-11963;
    • Other means of assembling vicinal quaternary carbon centers, based on radical-radical couplings, have been disclosed: a) K. M. Depew, S. P. Marsden, D. Zatorska, A. Zatorski, W. G. Bornmann, S. J. Danishefsky, J. Am. Chem. Soc. 1999, 121, 11953-11963;
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    • Alternatively referred to as a dihydroisoindigo
    • Alternatively referred to as a dihydroisoindigo.
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    • Ditriflate 39 has a shelf life of over one year when stored at -10°C.
    • Ditriflate 39 has a shelf life of over one year when stored at -10°C.
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    • Consistent with this interpretation, stereoselection was eroded in the presence of a sodium-selective cryptand (Kryptofix 221).
    • Consistent with this interpretation, stereoselection was eroded in the presence of a sodium-selective cryptand (Kryptofix 221).
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    • The translation of chirality from the electrophile to the quaternary stereocenter is influenced by the substituent at the 3-position of the oxindole, if LHMDS is used as the base. Intriguingly, when this substituent is changed from an oxindole enolate to a benzyl group, the quaternary stereocenter is installed in the corresponding product with the opposite relative configuration. A model to rationalize stereoinduction, when a benzyl group is the oxindole substituent has been proposed.[75
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    • For reviews focusing on catalytic asymmetric Heck reactions, see: d) M. Shibasaki, E. M. Vogl, T. Ohshima, Adv. Synth. Catal. 2004, 346, 1533-1552;
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    • Cyclizations of the ditriflate and diiodide substrates were carried out in opposite enantiomeric series. The enantiomer employed in the diiodide series is pictured
    • Cyclizations of the ditriflate and diiodide substrates were carried out in opposite enantiomeric series. The enantiomer employed in the diiodide series is pictured.
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    • For the initial reports of the asymmetric intramolecular Heck reaction, see: a
    • For the initial reports of the asymmetric intramolecular Heck reaction, see: a) Y. Sato, M. Sodeoka, M. Shibasaki, J. Org. Chem. 1989, 54, 4738-4739;
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    • At the outset, we entertained the possibility that this chemistry might be employed to attach a new pyrrolidino[2,3-b]indoline unit to either a preexisting pyrrolidino[2,3-b]indoline fragment or an oxindole precursor of such a unit. Both possibilities were examined. For several unanticipated reasons, the oxindole sequence turned out to be less attractive: a M. Oestreich, P. R. Dennison, J. J. Kodanko, L. E. Overman, Angew. Chem. 2001, 113, 1485-1489;
    • At the outset, we entertained the possibility that this chemistry might be employed to attach a new pyrrolidino[2,3-b]indoline unit to either a preexisting pyrrolidino[2,3-b]indoline fragment or an oxindole precursor of such a unit. Both possibilities were examined. For several unanticipated reasons, the oxindole sequence turned out to be less attractive: a) M. Oestreich, P. R. Dennison, J. J. Kodanko, L. E. Overman, Angew. Chem. 2001, 113, 1485-1489;
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    • For a recent survey of the use of palladium-catalyzed reactions in total synthesis, see
    • For a recent survey of the use of palladium-catalyzed reactions in total synthesis, see: K. C. Nicolaou, P. G. Bulger, D. Sarlah, Angew. Chem. 2005, 117, 4516-4563;
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    • As this was a model study, yields for the steps in sequence depicted in
    • As this was a model study, yields for the steps in sequence depicted in Scheme 20 were not optimized.
    • 20 were not optimized
    • Scheme1
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    • For examples of Stille cross-couplings at room temperature and the effect of tri-2-furylphosphine, see: V. Farina, B. Krishnan, J. Am. Chem. Soc. 1991, 113, 9585-9595;
    • For examples of Stille cross-couplings at room temperature and the effect of tri-2-furylphosphine, see: V. Farina, B. Krishnan, J. Am. Chem. Soc. 1991, 113, 9585-9595;
  • 142
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    • Ph.D. thesis, University of California, Irvine USA
    • a) J. J. Kodanko, Ph.D. thesis, University of California, Irvine (USA), 2003;
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    • Kodanko, J.J.1
  • 143
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    • Ph.D. thesis, University of California, Irvine USA
    • b) B. A. Stearns, Ph.D. thesis, University of California, Irvine (USA), 2000.
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    • 34547220648 scopus 로고    scopus 로고
    • For example, this structural feature is seen in X-ray structures of physostigmine; see: Cambridge Structural Database files QIHNEA and ESIRINIO.
    • For example, this structural feature is seen in X-ray structures of physostigmine; see: Cambridge Structural Database files QIHNEA and ESIRINIO.
  • 145
    • 34547161462 scopus 로고    scopus 로고
    • We have found recently that the inclusion of tert-butanol nearly doubles the yield of the final deprotection step; L. Sung unpublished results, UC Irvine, 2007.
    • We have found recently that the inclusion of tert-butanol nearly doubles the yield of the final deprotection step; L. Sung unpublished results, UC Irvine, 2007.
  • 147
    • 34547160952 scopus 로고    scopus 로고
    • A two-wheeled chariot drawn by four horses harnessed abreast, one representation of which sits atop Berlin's Brandenburg Gate.
    • A two-wheeled chariot drawn by four horses harnessed abreast, one representation of which sits atop Berlin's Brandenburg Gate.
  • 148
    • 34547159392 scopus 로고    scopus 로고
    • This number results from excluding less-stable stereoisomers in which the pyrrolidino[2,3-b]indoline rings are trans-fused
    • This number results from excluding less-stable stereoisomers in which the pyrrolidino[2,3-b]indoline rings are trans-fused.
  • 149
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    • For another example, see
    • For another example, see: E. Vedejs, O. Daugulis, J. Am. Chem. Soc. 1999, 121, 5813-5814.
    • (1999) J. Am. Chem. Soc , vol.121 , pp. 5813-5814
    • Vedejs, E.1    Daugulis, O.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.