Unprecedented (η5-Formylcyclohexadienyl)Mn(CO)3 Complexes: Synthesis, Structural and Theoretical Characterizations, and Resolution of the Planar Chirality

Autor:	Antoine Eloi, Hélène Gérard, Murielle Chavarot-Kerlidou, Béatrice Jacques, Patrick Herson, Françoise Rose-Munch, Eric Rose
Rok vydání:	2008
Předmět:	Steric effects chemistry.chemical_classification Stereochemistry Organic Chemistry Regioselectivity Planar chirality Aldehyde Inorganic Chemistry Benzaldehyde Crystallography chemistry.chemical_compound Enantiopure drug chemistry Nucleophile Reactivity (chemistry) Physical and Theoretical Chemistry
Zdroj:	Organometallics. 27:2505-2517
ISSN:	1520-6041 0276-7333
Popis:	The synthesis of the (η5-formylcyclohexadienyl)Mn(CO)3 complexes 5−8 was successfully achieved after lithiation and then electrophilic quench by DMF of variously substituted (η5-cyclohexadienyl)Mn(CO)3 complexes. Their full experimental characterization is reported, together with a theoretical study that allowed the consequences of the regiochemistry on the electronic properties of the complexes to be understood. Rearomatization of complex 6 led to the formation of the cationic [(η6-2-methoxybenzaldehyde)Mn(CO)3]+ complex 11, first example of a benzaldehyde derivative coordinated to the Mn(CO)3+ entity. The electrophilic reactivity of the formyl group of complex 5 was tested with hydrides and a Grignard reagent as the nucleophiles. The corresponding alcohols were isolated in high yields and the excellent diastereoselectivity could be explained by steric factors clearly identified thanks to the crystal structure determination of the starting aldehyde 7b. By using the enantiopure (R,R)-N,N′-dimethylcyclohex...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::5e6d294cac671153eb0d07f5bb7c7812 https://doi.org/10.1021/om7012666 Zobrazit plný text záznamu