Selective syntheses with organometallics. Part XI. An efficient synthesis of a,b-unsaturated aldehydes by a four-carbon unit extension of Grignard reagents
Oxirane I, prepd. by epoxidn. of (EtO)2CHCH2CH:CH2, reacted with Grignard reagents in the presence of catalytic CuBr to give 78-92% b-hydroxyacetals (EtO)2CHCH2CHR1OH [II; R1 = CH2CMe3, CH2CHMeEt, pentyl, CH2CH2CMe:CH2, CH2Ph, CH2CH2Ph, (CH2)7OR2; R2 = tetrahydropyranyl, SiMe3], which gave enals HCOCH:CHR1 in 50-85% yield on hydrolysis. Careful hydrolysis of II (R1 = CH2CMe3) gave HCOCH2CHR1OH, which formed H2C:CHCH2CHR1OH on Wittig reaction or dimerized to form 1,3-dioxane III. [on SciFinder (R)]
1984
67
6
1470
4
CAN 102:78320
23-15
Aliphatic Compounds
Inst. Chim. Org.,Univ. Lausanne,Lausanne,Switz.
Journal
written in English.
78-86-4; 100-44-7; 108-86-1; 109-65-9; 507-20-0; 563-47-3; 2009-84-9 Role: RCT (Reactant), RACT (Reactant or reagent) (Grignard reaction of, with (diethoxyethyl)oxirane, hydroxyacetal and unsatd. aldehyde by); 122-51-0 Role: RCT (Reactant), RACT (Reactant or reagent) (Grignard reaction of, with allyl chloride); 107-05-1 Role: RCT (Reactant), RACT (Reactant or reagent) (Grignard reaction of, with tri-Et orthoformate); 3487-44-3; 19493-09-5 Role: RCT (Reactant), RACT (Reactant or reagent) (Wittig reaction of, with hydroxyhexanal); 7787-70-4 Role: CAT (Catalyst use), USES (Uses) (catalysts, for Grignard reaction of (diethoxyethyl)oxirane); 13269-78-8P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and Grignard reaction of, hydroxyacetals and unsatd. aldehydes by); 34714-00-6P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and Grignard reaction of, with (diethoxyethyl)oxirane); 94705-06-3P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and dimerization and Wittig reaction of); 10602-36-5P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and epoxidn. of); 91525-86-9P; 94705-01-8P; 94705-02-9P; 94705-03-0P; 94705-04-1P; 94705-05-2P; 94705-07-4P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of); 2363-89-5P; 13910-23-1P; 33046-84-3P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of, via Grignard reaction of oxirane); 94704-94-6P; 94704-95-7P; 94704-96-8P; 94704-97-9P; 94704-98-0P; 94704-99-1P; 94705-00-7P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn., hydrolysis, and dehydration of); 2009-83-8 Role: RCT (Reactant), RACT (Reactant or reagent) (silylation of)
REVIEWED
EPFL