Intramolecular Nucleophilic Acyl Substitution Reaction of 3,4-Alkadienyl Carbonates Mediated by Ti(O-i-Pr)4/2 i-PrMgCl Reagent. Efficient Synthesis of Optically Active β,γ-Unsaturated Esters with an α-Substituent
- 1 January 1996
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 61 (22), 7826-7831
- https://doi.org/10.1021/jo961401t
Abstract
Treatment of 3,4-alkadienyl carbonates 2a-i with a low-valent titanium reagent diisopropoxy(eta(2)-propene)titanium (1), readily generated by the reaction of Ti(O-i-Pr)(4) with 2 i-PrMgCl, resulted in an intramolecular nucleophilic acyl substitution (INAS) reaction to afford vinyltitanium compounds 3 which, in turn, reacted with H(3)O(+), D(2)O, or iodine to give alpha-substituted beta,gamma-unsaturated esters 4 in good to excellent yields. The olefin moiety of the hydrolysis product 4 has (Z)-geometry mainly except for 4h. Starting from chiral 2f or 2g, the reaction proceeded stereospecifically to give optically active alpha-substituted beta,gamma-unsaturated ester 4f or 4g having (Z)-olefin geometry exclusively.Keywords
This publication has 21 references indexed in Scilit:
- Structure and Asymmetric Diels−Alder Reactions of Optically Active Allene-1,3-dicarboxylatesThe Journal of Organic Chemistry, 1996
- Intramolecular Nucleophilic Acyl Substitution Reactions Mediated by XTi(O-i-Pr)3 (X = Cl, O-i-Pr)/2i-PrMgBr Reagent. Efficient Synthesis of Functionalized Organotitanium Compounds from Unsaturated CompoundsJournal of the American Chemical Society, 1996
- Intramolecular Hydroxycyclopropanation of ω-Vinyl Carboxylic EstersJournal of the American Chemical Society, 1996
- Synthesis of allyltitanium compounds by intramolecular nucleophilic acyl substitution reaction of alka-3,5-dienyl carbonates and their unusual regioselectivity in reaction with aldehydesChemical Communications, 1996
- Total Synthesis of the Unusual Marine Alkaloid (-)-Papuamine Utilizing a Novel Imino Ene ReactionJournal of the American Chemical Society, 1995
- New, Efficient Method for the Synthesis of Allyltitanium Compounds from Allyl Halides or Allyl Alcohol Derivatives via Oxidative Addition. A Highly Efficient and Practical Synthesis of Homoallyl AlcoholsJournal of the American Chemical Society, 1995
- Synthesis of (.+-.)-7,8-epoxy-4-basmen-6-one by a transannular cyclization strategyJournal of the American Chemical Society, 1993
- On the maximum rotation and the solvobromination and -mercuration of enantioenriched 1,3-dimethylalleneThe Journal of Organic Chemistry, 1991
- Synthesis and stereochemistry of allenes. Part 3. Highly stereoselective synthesis of chiral alkyl allenes by organocopper(I)-induced anti 1,3-substitution of chiral propynyl estersThe Journal of Organic Chemistry, 1989
- Synthesis and Absolute Configuration of (+)-Phrymarolin I, a LignanChemistry Letters, 1986