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4544256551
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1H NMR analysis of the crude reaction mixture failed to identify any of the independently prepared diastereomeric nitrile.
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20
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0000232576
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Methylation of 3b corresponds to a retentive alkylation of the chiral C-magnesiated nitrile, as consistently observed in the inter- and intramolecular alkylations (Table 1). The retentive alkylations of 3b contrast with invertive acylations of a closely related magnesiated nitrile[8] implying an unusual electrophile-dependent stereoselectivity analogous to that observed with selected chiral organolithium reagents.[a] Interception of 3b with a range of electrophiles is being pursued to determine if the alkylation stereoselectivity of this magnesiated nitrile is indeed electrophile dependent. a) A. Basu, S. Thayumanavan Angew. Chem. 2002, 114, 740; Angew. Chem. Int. Ed. 2002, 41, 717.
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85080848774
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Methylation of 3b corresponds to a retentive alkylation of the chiral C-magnesiated nitrile, as consistently observed in the inter- and intramolecular alkylations (Table 1). The retentive alkylations of 3b contrast with invertive acylations of a closely related magnesiated nitrile[8] implying an unusual electrophile-dependent stereoselectivity analogous to that observed with selected chiral organolithium reagents.[a] Interception of 3b with a range of electrophiles is being pursued to determine if the alkylation stereoselectivity of this magnesiated nitrile is indeed electrophile dependent. a) A. Basu, S. Thayumanavan Angew. Chem. 2002, 114, 740; Angew. Chem. Int. Ed. 2002, 41, 717.
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4544309313
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X-ray crystallography of 4b and 4c confirmed the stereochemical assignment. CCDC-218678 (4b) and CCDC-218679 (4c) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam. ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ccdc.cam.ac.uk).
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4544350009
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b) Commercially available from Lancaster.
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30
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4544288601
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note
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Cyclization affords a 9:1 ratio of cis:trans abietanes in favor of 9.
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-
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31
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0026025949
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4544275622
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note
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b) A 13% yield of the carbocyclic ester is formed from a carbocationic cyclization from the corresponding alkene.[18a]
-
-
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33
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0000559891
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epi-Abietic: acid 10 is used as a biological marker for diterpenoids[21a] in geochemical sediments and has been previously synthesized.[21b,c] a) B. R. T. Simoneit, Geochim. Cosmochim. Acta 1977, 41, 463;
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