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Volumn 13, Issue 13, 2007, Pages 3739-3756

Stille-heck coupling sequences applied in a versatile new access to steroid skeletons

Author keywords

Asymmetric catalysis; Cross coupling; Palladium; Pericyclic reactions; Steroids

Indexed keywords

CATALYSTS; CYCLIZATION; PALLADIUM; SUBSTITUTION REACTIONS; SYNTHESIS (CHEMICAL);

EID: 34250651657     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200601240     Document Type: Article
Times cited : (25)

References (75)
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    • For an alternative approach to certain steroidal compounds with an assembly of the B-ring by two consecutive Heck couplings, see refs, 2o,p] as well as: L. F. Tietze, S. Peterson, Chem. 2001, 1619-1624, and references therein
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    • For reviews on the Heck reaction see: a, Eds, A. de Meijere, F. Diederich, Wiley VCH, Weinheim
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    • Heck coupling protocols on the basis of Pd(OAc)2 and phosphane ligands as triphenylphosphane, other trisarylphosphanes as tris-o-tolylphosphane and tris-n-butylphosphane with different solvent systems and bases were investigated.
    • Heck coupling protocols on the basis of Pd(OAc)2 and phosphane ligands as triphenylphosphane, other trisarylphosphanes as tris-o-tolylphosphane and tris-n-butylphosphane with different solvent systems and bases were investigated.
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    • The beneficial role of water as a co-solvent in Heck reactions has previously been established, a N. A. Bumagin, N. P. Andryukhova, I. P Beletskaya, Izv. Akad. Nauk USSR, Ser. Khim. 1988, 1449-1450;
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    • 1H NOESY experiments in which interactions within the steroid analogue cis-13b between the protons of the methyl group at C-13 and the proton at C-14 as well as between the proton at C-14 with the proton at C-7 were detected. Within the steroid trans-24b interactions between the methyl group at C-13 and the proton at C-8 could be observed and also interactions between the proton at C-7 with the proton at C-8 and the proton at C-14 with one proton at C-15 were found.
    • 1H NOESY experiments in which interactions within the steroid analogue cis-13b between the protons of the methyl group at C-13 and the proton at C-14 as well as between the proton at C-14 with the proton at C-7 were detected. Within the steroid trans-24b interactions between the methyl group at C-13 and the proton at C-8 could be observed and also interactions between the proton at C-7 with the proton at C-8 and the proton at C-14 with one proton at C-15 were found.
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    • this rotational selectivity has also been termed torquoselectivity. cf
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    • CCDC-618817 (trans-27) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/ data_request/cif/
    • CCDC-618817 (trans-27) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/ data_request/cif/
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    • CCDC-618818 (33) contains the supplementary Crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif/
    • CCDC-618818 (33) contains the supplementary Crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif/
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    • CCDC-618819 (37) contains the supplementary Crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam. ac.uk/data_request/cif/
    • CCDC-618819 (37) contains the supplementary Crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam. ac.uk/data_request/cif/
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    • The methyl ester analogue of compound trans-27 was obtained along the same synthetic pathway, using the less cleanly and efficiently reacting methyl acrylate instead of tert-butyl acrylate in the Heck reaction.
    • The methyl ester analogue of compound trans-27 was obtained along the same synthetic pathway, using the less cleanly and efficiently reacting methyl acrylate instead of tert-butyl acrylate in the Heck reaction.


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