Biomedical subjects
Publications and source records attributed to Laurence Grimaud.
The three-component addition of isocyanides to phenol derivatives and aldehydes proceeds easily in methanol to form O-arylated compounds in a new Passerini-type reaction. The key step of the conversion lies in an irreversible Smiles rearrangement of intermediate phenoxyimidate adducts. It represents the first use of a Smiles rearrangement in a Passerini reaction. [reaction: see text]
New heterocyclic scaffolds can be easily prepared by the coupling of heteroaromatic phenols (pyridines, pyrimidines) with carbonyl compounds, amines, and isocyanides. This transformation related to the Ugi reaction probably involves a Smiles rearrangement. The scope of this methodology is further extended by the successful use of heterocyclic thiols to form highly functionalized thioamides.
Herein, we wish to report a new three-component formation of heterocyclic scaffolds based on a one-pot process from simple phenols. The key step of this procedure involves an ortho-quinone methide formation from Mannich adducts under alkylative conditions. The transient o-quinone methide has been trapped in situ with indole and diketone using lithium perchlorate as catalyst. The interest of this procedure has been furthermore demonstrated by a new three-component aminobenzofuran formation from phenols, aldehydes and isocyanides.
Explore the source record for details and available documents.
[reaction: see text] N-Monosubstituted carbamates are cleanly converted to amides under treatment with trialkylaluminum. This reaction involves an aluminum-assisted internal delivery of alkyl groups. It can be applied to new and mild protecting group strategies for alcohols.
Trimethylaluminum addition to N-monoalkyl or N-monoaryl hydrazones followed by aldehyde addition leads to the formation of N-alkylated hydrazones in a new formal Mannich-type process. Addition compounds were also obtained in moderate yields with ketones. The mechanism as well as possible intermediates involved in the reaction are discussed.
[reaction: see text] A selective domino ring-closing metathesis (RCM)-cross-metathesis (CM) process between enynes and electron-deficient alkenes is reported. The conditions have been optimized for enynes 3 and methyl acrylate with catalyst IV. The scope and limitations of this reaction are described, and a possible mechanism is discussed.
We have designed a new method to make synthons encompassing a protected syn 1,3-diol motif and an aldehyde alpha to the 1,3-dioxane ring. An additional stereocenter was also created, potentially leading to stereochemically defined 1,2,4-triols. This method was successfully applied to the synthesis of the C16-C24 portion of Dolabelides.