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Volumn 45, Issue 3, 2006, Pages 440-444

Unusual structure and reactivity of a homoleptic "super-ate" complex of iron: Implications for Grignard additions, cross-coupling reactions, and the Kharasch deconjugation

Author keywords

Ate complexes; Cross coupling; Grignard reaction; Iron; Single electron transfer

Indexed keywords

MOLECULES; REACTION KINETICS;

EID: 30444440562     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200502859     Document Type: Article
Times cited : (136)

References (93)
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    • Pioneering studies on the use of iron for cross-couplings: a) M. Tamura, J. K. Kochi, J. Am. Chem. Soc. 1971, 93, 1487-1489;
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    • note
    • Attempted crystallizations are reported in ref. [9].
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    • -3. CCDC-279956 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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    • note
    • The four independent C-Fe-C angles are 113.67(15), 109.24(9), 109.28(9), and 105.83(15)°.
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    • note
    • The standard uncertainty of the average edge is within three times the average standard uncertainties of each individual edge.
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    • note
    • 4 is 2.31(5) Å, the average C-Li distance in 1 is 2.25(6) Å.
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    • d) for a review on iron-alkyl species carrying extra stabilizing ligands, see: A. Yamamoto, J. Organomet. Chem. 1986, 300, 347-367.
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    • see Scheme 4
    • Although GC shows seemingly clean conversions, the isolated yields of 5 remained disappointingly low using either defined 1 or the in situ system, see Scheme 4.
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    • Complex 1, however, seems to be unable to transfer electrons to dialkyl ketones as evident from the clean addition to 4-tert-butylcyclohexanone. This result is again in excellent agreement with the report by Ashby et al. who showed that the iron content in the magnesium has no effect in Grignard additions to aliphatic carbonyl compounds. Moreover, they are in line with the finding that certain iron salts beneficially effect the stereoselective course of addition of cyclic ketones as reported by Reetz et al., see: M. T. Reetz, S. Stanchev, J. Chem. Soc. Chem. Commun. 1993, 328-330.
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    • note
    • 3): δ = 200.5, 145.2, 142.0, 141.9, 135.2, 31.9, 29.7, 19.5, 19.4, 15.5 ppm.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.