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Selective syntheses with organometallics. VI. Capricious stereoselectivities of alkenylpotassium formation under kinetic and thermodynamic control. Oxygen-triggered configurational equilibration of an allyl type organometallic compound

Metalation at the allylic site (Me group) of (Z)-RCH:CHMe (R = alkyl) is more rapid than with the E-isomers regardless of the configuration in which the resultant organometallic is more thermodn. stable. Thus, (Z)-Me3CCH:CHCH2K is formed 15 times faster than its E-isomer, although the latter is thermodn. favored. Isomerization of the allylpotassium compds. in THF is very slow, but may be catalyzed by trace impurities, e.g., O. [on SciFinder (R)]

    Keywords: Metalation (of allylic alkenes); Isomerization (of metalated allylic alkenes); Alkenes Role: RCT (Reactant) ; RACT (Reactant or reagent) (allyl ; metalation of) ; metalation propene deriv kinetics; allylpotassium isomerization

    Note:

    CAN 87:133729

    22-9

    Physical Organic Chemistry

    Inst. Chim. Org.,Univ. Lausanne,Lausanne,Switz.

    Journal

    0018-019X

    written in English.

    690-08-4; 4050-45-7 Role: RCT (Reactant), RACT (Reactant or reagent) (metalation of, followed by reaction with oxirane); 64172-07-2P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. and conversion to tert-butylpentenal); 64172-10-7P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and reaction with pivalaldehyde); 64172-08-3P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. and redn. of aldehyde group to alc. group in); 64081-43-2P; 64081-44-3P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. and vinylation of hydroxy group in); 31502-21-3P; 54393-36-1P; 64172-09-4P; 64172-11-8P; 64172-12-9P; 64172-13-0P; 64172-14-1P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of); 630-19-3 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with (hydroxybutyl)triphenylphosphonium chloride); 603-35-0 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with 4-chloro-1-butanol); 762-63-0 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with butyllithium); 109-72-8 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with dimethylpentene); 75-21-8 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with metalated propene derivs.); 110-87-2 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with tert-butyllithium); 928-51-8 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with triphenylphosphine)

    Reference

    • LSCO-ARTICLE-1977-005

    Record created on 2006-03-03, modified on 2016-08-08

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