TY - JOUR
T1 - Two substrates, three products
T2 - Reactions between ferrocene-carboxaldehyde and dioxaphospholene, characterization and crystal structures of oxygenated C3- and C4-chain-containing ferrocenes
AU - Ahumada, Guillermo
AU - Hamon, Paul
AU - Dorcet, Vincent
AU - Roisnel, Thierry
AU - Manzur, Carolina
AU - Carrillo, David
AU - Soto, Juan Pablo
AU - Hamon, Jean René
N1 - Funding Information:
The authors thank Drs M. Fuentealba (PUCV Valparaíso), S. Sinbandhit and P. Jehan (CRMPO, Rennes) for assistance with graphical treatment of crystallographic data, NMR and HRMS experiments, respectively. This research has been performed as part of the Chilean-French International Associated Laboratory for “Inorganic Functional Materials” (LIAMIF-CNRS N°836). Financial support from the Fondo Nacional de Desarrollo Científico y Tecnológico [FONDECYT (Chile), grant no. 1090310 (C.M. and D.C.)], the Vicerrectoría de Investigación y Estudios Avanzados, Pontificia Universidad Católica de Valparaíso , Chile (C.M. and D.C.), the CNRS and the Université de Rennes 1 is gratefully acknowledged. G.A. Thanks the CONICYT (Chile) for support of a graduate fellowship.
PY - 2013/5/15
Y1 - 2013/5/15
N2 - Reactions of aldehydes RCHO with 2,2,2-trimethoxy-4,5-dimethyl-1,3,2- dioxaphospholene are known to form trimethylbiacetyl-aldehyde-phosphite adducts which upon methanolysis gave rise to the corresponding symmetrical 3-R-2,4-pentanediones (R = aryl, alkyl). Reactions between ferrocenecarboxaldehyde and the biacetyl-trimethylphosphite adduct, whatever the experimental conditions used, afforded three new oxygenated C3 and C4 side-chain containing ferrocenyl complexes, namely, 1-ferrocenyl-1,2-propanedione (1, Fc-C(O)C(O)CH3; Fc = (η5-C5H5)Fe(η5-C 5H4)), 4-methoxy-4-ferrocenyl-3-hydroxy-3-methyl-2- butanone (2, Fc-CH(OCH3)C(CH3)(OH)C(O)CH3) as a single diastereoisomer, and the ferrocenyl enone 4-ferrocenyl-3-methyl-3-buten- 2-one (3, Fc-CHC(CH3)C(O)CH3) with the enone portion adopting the s-trans conformation in the solid state. The compounds readily purified by silica gel packed column chromatography were isolated in 31-44% yields, and their constitution is in agreement with elemental analyses, IR and multinuclear NMR spectroscopy, and electrospray mass spectrometry. Their molecular identity and geometry have been confirmed by single-crystal X-ray diffraction.
AB - Reactions of aldehydes RCHO with 2,2,2-trimethoxy-4,5-dimethyl-1,3,2- dioxaphospholene are known to form trimethylbiacetyl-aldehyde-phosphite adducts which upon methanolysis gave rise to the corresponding symmetrical 3-R-2,4-pentanediones (R = aryl, alkyl). Reactions between ferrocenecarboxaldehyde and the biacetyl-trimethylphosphite adduct, whatever the experimental conditions used, afforded three new oxygenated C3 and C4 side-chain containing ferrocenyl complexes, namely, 1-ferrocenyl-1,2-propanedione (1, Fc-C(O)C(O)CH3; Fc = (η5-C5H5)Fe(η5-C 5H4)), 4-methoxy-4-ferrocenyl-3-hydroxy-3-methyl-2- butanone (2, Fc-CH(OCH3)C(CH3)(OH)C(O)CH3) as a single diastereoisomer, and the ferrocenyl enone 4-ferrocenyl-3-methyl-3-buten- 2-one (3, Fc-CHC(CH3)C(O)CH3) with the enone portion adopting the s-trans conformation in the solid state. The compounds readily purified by silica gel packed column chromatography were isolated in 31-44% yields, and their constitution is in agreement with elemental analyses, IR and multinuclear NMR spectroscopy, and electrospray mass spectrometry. Their molecular identity and geometry have been confirmed by single-crystal X-ray diffraction.
KW - Enone
KW - Ferrocene
KW - Hydroxyketone
KW - X-ray structure
KW - α-Diketone
UR - http://www.scopus.com/inward/record.url?scp=84874935068&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2013.02.017
DO - 10.1016/j.jorganchem.2013.02.017
M3 - Article
AN - SCOPUS:84874935068
SN - 0022-328X
VL - 732
SP - 40
EP - 46
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
ER -