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Volumn 69, Issue 12, 2004, Pages 4152-4158

Stereoselective synthesis of atropisomeric korupensamines A and B utilizing planar chiral arene chromium complex

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL BONDS; COMPLEXATION; ISOMERIZATION; ORGANIC ACIDS; SYNTHESIS (CHEMICAL);

EID: 2942616766     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo049600x     Document Type: Article
Times cited : (64)

References (123)
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    • note
    • 3)) of de-tricarbonylchromium compound derived from thermally isomerized anti-biaryl chromium complex 14 by air oxidation was completely identical with that of de-tricarbonylchromium compound of the syn-biaryl complex 13.
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    • note
    • D +65 (c 0.76, MEOH): see ref 11d.
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    • Enantiomerically pure (+)-2-bromo-3,5-difluorobenzaldehyde chromium complex (37) was obtained by optical resolution of the diastereomers prepared from the corresponding racemic chromium complex and L-valinol with column chromatography according to reported procedure: (a) Davies, S. G.; Goodfellow, C. L. J. Chem. Soc., Perkin Trans 1 1989, 192.
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    • note
    • Reflux of difluoro-substituted syn-biaryl chromium complex 39 in a mixture of di-n-butyl ether and dichloroethane resulted in recovery of the starting material without tricarbonylchromium migration to the inverted arene face despite the benzyl alcohol function. This result would be attributed to the strong electron-withdrawing ability of the fluorine atom: see ref 24.
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    • note
    • Nucleophilic substitution reaction of the fluoro atom of 41 with sodium isopropoxide gave a complex mixture. The formyl group of 41 disappeared in this nucleophilc substitution reaction. Furthermore, nucleophilic substitution of an anti-difluorobenzyl alcohol chromium complex obtained from 41 by sodium borohydride reduction gave a monoisopropoxy-substituted chromium complex under the same conditions with syn-biaryl chromium complex 39. The ortho-fluorine atom of the anti-biaryl chromium complex did not reacted with the nucleophile due to steric hindrance.


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