The abnormal behavior of an atropisomer: 3,3'-dibromo-1,1'-difluoro-2,2'-binaphthyl reacting with alkyllithium compounds
1-Fluoro-2-(triethylsilyl)naphthalene and other 1-fluoronaphthalene derivs. bearing a metalation-resistant substituent at the 2-position proved to be totally inert toward base attack. 3-Bromo-1-fluoronaphthalene, readily prepd. from a 2-bromo isomer by deprotonation-triggered heavy halogen migration, was converted into 3,3'-dibromo-1,1'-difluoro-2,2'-binaphthyl (I) by consecutive treatment with lithium diisopropylamide, copper(II) bromide and nitrobenzene. The dilithiated intermediate generated from the atropisomer I by treatment with 2 equiv. of butyllithium reacted with a variety of electrophiles to afford products such as, diacid or bis(phosphane) derivs. . in high yields. The latter compd. was also obtained in a straightforward manner from (4-fluoro-2-naphthyl)diphenylphosphine oxide. Unexpectedly, neither the 3,3'-dibromobinaphthyl I nor its 3,3'-diiodo analog were amenable to a unilateral but only to a double-sided halogen/metal permutation. [on SciFinder (R)]
WOS:000233713100015
2005
23
5049
5054
25-24 Benzene, Its Derivatives, and Condensed Benzenoid Compounds Laboratoire de Stereochimie (CNRS UMR 7509),Universite Louis Pasteur (ECPM),Strasbourg,Fr. Journal 1434-193X written in English. 874907-59-2P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of (fluoro)(iodo)binaphthalene deriv., study of reaction of (fluoro)naphthalene and study of behavior of atropisomer dibromo-difluoro-binaphthalene with alkyllithium compds.); 874907-48-9P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. of bromo(fluoro)(iodo)naphthalene and related study of reaction of (fluoro)naphthalene and atropisomer deriv. dibromo-difluoro-binaphthalene with alkyllithium compds.); 317-79-3P; 13772-59-3P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. of bromo(fluoro)naphthalene and related study of reaction of (fluoro)naphthalene and atropisomer deriv. dibromo-difluoro-binaphthalene with alkyllithium compds.); 874907-52-5P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of dibenzofluorenone and related study of reaction of (fluoro)naphthalene and atropisomer deriv. dibromo-difluoro-binaphthalene with alkyllithium compds.); 874907-49-0P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. of dibromo-difluoro-2,2'-binaphthyl and related study of reaction of atropisomer deriv. with alkyllithium compds.); 874907-55-8P; 874907-56-9P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of difluoro(phosphinyl)binaphthalene deriv., study of reaction of (fluoro)naphthalene and study of behavior of atropisomer dibromo-difluoro-binaphthalene with alkyllithium compds.); 874907-50-3P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. of difluoro-2,2'-binaphthalene dicarboxaldehyde and related study of reaction of (fluoro)naphthalene and atropisomer deriv. dibromo-difluoro-binaphthalene with alkyllithium compds.); 874907-53-6P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of difluoro-2,2'-binaphthalene dicarboxylic acid and related study of reaction of (fluoro)naphthalene and atropisomer deriv. dibromo-difluoro-binaphthalene with alkyllithium compds.); 874907-51-4P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of difluoro-2,2'-binaphthalene dimethanol and related study of reaction of (fluoro)naphthalene and atropisomer deriv. dibromo-difluoro-binaphthalene with alkyllithium compds.); 874907-47-8P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. of difluoro-2,2'-binaphthyl and related study of reaction of (fluoro)naphthalene and atropisomer deriv. dibromo-difluoro-binaphthalene with alkyllithium compds.); 874907-54-7P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of difluoro-binaphthalene deriv., study of reaction of (fluoro)naphthalene and study of behavior of atropisomer dibromo-difluoro-binaphthalene with alkyllithium compds.); 874907-58-1P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of fluoro(phosphinyl)binaphthalene oxide deriv., study of reaction of (fluoro)naphthalene and study of behavior of atropisomer dibromo-difluoro-binaphthalene with alkyllithium compds.); 874907-57-0P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. of fluoro(phosphinyl)naphthalene oxide deriv., study of reaction of (fluoro)naphthalene and study of behavior of atropisomer dibromo-difluoro-binaphthalene with alkyllithium compds.); 874907-45-6P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. of fluoro(triethylsilyl)naphthalene and related study of reaction of (fluoro)naphthalene and atropisomer deriv. dibromo-difluoro-binaphthalene with alkyllithium compds.); 143901-96-6P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of fluoro-naphthalenecarboxaldehyde and related study of reaction of (fluoro)naphthalene and atropisomer deriv. dibromo-difluoro-binaphthalene with alkyllithium compds.); 874907-46-7P Ro e: SPN (Synthetic preparation), PREP (Preparation) (prepn. of tris[(fluoro)naphthalenyl]phosphine and related study of reaction of (fluoro)naphthalene and atropisomer deriv. dibromo-difluoro-binaphthalene with alkyllithium compds.); 109-72-8 (Butyllithium); 321-38-0; 594-19-4 (tert-Butyllithium); 598-30-1; 644-97-3; 994-30-9; 1079-66-9 (Chlorodiphenylphosphine); 1499-21-4 (Diphenylphosphinic chloride); 16523-54-9 Role: RCT (Reactant), RACT (Reactant or reagent) (study of reaction of (fluoro)naphthalene and related study of behavior of atropisomer dibromo-difluoro-binaphthalene with alkyllithium compds.)
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