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Insights into the Cerium Chloride‐Catalyzed Grignard Addition to Esters
Author(s) -
Conlon David A.,
Kumke Daniel,
Moeder Charles,
Hardiman Michelle,
Hutson Gerri,
Sailer Laura
Publication year - 2004
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200404075
Subject(s) - chemistry , cerium , chloride , anhydrous , ketone , catalysis , nucleophile , grignard reaction , medicinal chemistry , alcohol , organic chemistry , inorganic chemistry , reagent
Addition of methylmagnesium chloride to ester 1 in the presence of cerium chloride gave significantly better yields of the tertiary alcohol 2 than the reaction performed in the absence of cerium chloride. The beneficial effect of added cerium chloride is postulated to be due to suppression of the enolization of the ketone intermediate. The use of properly “activated” anhydrous cerium chloride which is proposed to generate a less basic, more nucleophilic species to overcome this undesired reaction was found to be critical. The activated cerium chloride was identified as the known seven‐coordinate THF solvate, [CeCl(μ‐Cl) 2 (THF) 2 ] n . Inactive crystal forms were also identified and the key parameters for formation of the active form were delineated.