Pentadienyl type lithium and potassium species: the regioselectivity of their reactions with electrophiles

Seven structurally distinct pentadienyl type lithium and potassium compds. were screened against a variety of electrophiles in order to assess the regioselectivity of the trapping reactions. Organoborates and analogs thereof (fluorodimethoxyborane) proved to be perfectly regio-reliable attacking only unsubstituted terminal positions and thus providing, after oxidn., exclusively primary allylic alcs. 2,4-Pentadienyllithiums or -potassiums, that carry a Me group at the 1- or 3-position, exhibit the same extreme regioselectivity towards halotrialkylsilanes or carbon dioxide. Although the unsubstituted parent compds. combine with such electrophiles still preferentially at the terminal position, considerable proportions of branched products are concomitantly formed as well (1/3-attack ratios ranging from 2:1 to > 20:1). Hydroxyalkylating and alkylating reagents such as formaldehyde, oxirane or Bu iodide invariably afford regioisomeric mixts. generally varying in compn. between 3:1 and 1:3. The condensation reaction with halotrialkylsilanes appears to follow a concerted (SN2-like) rather than an addn./elimination (ate complex mediated) mechanism. [on SciFinder (R)]

Published in:
Synthesis, 12, 1830-1836
CAN 136:53781
Organometallic and Organometalloidal Compounds
Section de Chimie, BCh,Universite Lausanne,Lausanne,Switz.
written in English.
51391-25-4 (2,4-Pentadienylpotassium); 74206-00-1; 383176-69-0; 383176-70-3 Role: FMU (Formation, unclassified), RCT (Reactant), FORM (Formation, nonpreparative), RACT (Reactant or reagent) (formation and regiochem. of metalation and sequential reaction with electrophiles); 383176-90-7; 383176-91-8 Role: RCT (Reactant), RACT (Reactant or reagent) (formation and regiochem. of metalation and sequential reaction with electrophiles); 87832-31-3 (prepn. of); 32775-96-5P; 32793-94-5P; 79210-76-7P; 95421-98-0P; 102787-31-5P; 102787-32-6P; 139377-12-1P; 139377-13-2P; 139377-14-3P; 383176-71-4P; 383176-72-5P; 383176-73-6P; 383176-74-7P; 383176-75-8P; 383176-76-9P; 383176-77-0P; 383176-78-1P; 383176-79-2P; 383176-80-5P; 383176-81-6P; 383176-82-7P; 383176-83-8P; 383176-84-9P; 383176-85-0P; 383176-86-1P; 383176-88-3P; 383176-89-4P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of); 591-93-5 (1,4-Pentadiene); 1115-08-8 (3-Methyl-1,4-pentadiene); 7318-67-4 (cis-1,4-Hexadiene); 7319-00-8 (trans-1,4-Hexadiene); 51755-96-5 (2,7-Dimethyl-2,6-heptadiene) Role: RCT (Reactant), RACT (Reactant or reagent) (regiochem. of metalation and sequential reaction with electrophiles); 75-21-8 (Oxirane); 75-77-4 (Chlorotrimethylsilane); 367-46-4 (Fluorodimethoxyborane); 420-56-4 (Fluorotrimethylsilane); 994-30-9 (Chlorotriethylsilane); 1195-66-0; 2857-97-8 (Bromotrimethylsilane); 13154-24-0 (Chlorotriisopropylsilane); 16029-98-4 (Iodotrimethylsilane); 25267-27-0 (Iodobutane) Role: RCT (Reactant), RACT (Reactant or reagent) (regioselectivity of reactions of pentadienyl type lithium and potassium species with electrophiles)

 Record created 2006-03-03, last modified 2018-01-27

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