57784-11-9Relevant articles and documents
Stereospecific Asymmetric Synthesis of Tertiary Allylic Alcohol Derivatives by Catalytic [2,3]-Meisenheimer Rearrangements
Yu, Xin,Wannenmacher, Nick,Peters, René
supporting information, p. 10944 - 10948 (2020/05/04)
Chiral acyclic tertiary allylic alcohols are very important synthetic building blocks, but their enantioselective synthesis is often challenging. A major limitation in catalytic asymmetric 1,2-addition approaches to ketones is the enantioface differentiation by steric distinction of both ketone residues. Herein we report the development of a catalytic asymmetric Meisenheimer rearrangement to overcome this problem, as it proceeds in a stereospecific manner. This allows for high enantioselectivity also for the formation of products in which the residues at the generated tetrasubstituted stereocenter display a similar steric demand. Low catalyst loadings were found to be sufficient and the reaction conditions were mild enough to tolerate even highly reactive functional groups, such as an enolizable aldehyde, a primary tosylate, or an epoxide. Our investigations suggest an intramolecular rearrangement pathway.
Biotransformation of (-)-dihydromyrcenyl acetate using the plant parasitic fungus Glomerella cingulata as a biocatalyst
Miyazawa,Akazawa,Sakai,Nankai
, p. 4826 - 4829 (2007/10/03)
The microbial transformation pf (-)-dihydromyrcenyl acetate was investigated using the plant parasitic fungus Glomerella cingulata. As a result, (-)-dihydromyrcenyl acetate was converted to dihydromyrcenol, 3,7-dihydroxy-3,7-dimethyl-1-octene-7-carboxylate, 3,7-dihydroxy-3,7-dimethyl-1-octene, 3,7-dimethyloctane-1,2,7-triol-7-carboxylate, and 3,7-dimethyloctane-1,2,7-triol. In addition, microbial transformation of dihydromyrcenol by G. cingulata was carried out. The metabolic pathway of (-)-dihydromyrcenyl acetate is discussed.
Micellar-Induced Selectivity and Rate Enhancement in the Acid-Catalyzed Cyclization and Rearrangement of Monoterpenes. The Solvolysis of Linalyl and Geranyl Acetates
Clark, Benjamin C.,Chamblee, Theresa S.,Iacobucci, Guillermo A.
, p. 1032 - 1036 (2007/10/02)
The monoterpene linalyl acetate (1) undergoes acid-catalyzed solvolysis/cyclization at pH 3 in HCl/citrate buffer to yield three major acyclic alcohols, geranol (2), linalool (3), and nerol (4), and one cyclic alcohol, α-terpineol (5).The acyclic/cyclic alcohol ratio is 2.7 in no sodium dodecyl sulfate (SDS) controls after ca. 3 half-lives, compared to 8.5 when the reaction is carried out in a SDS micelle.No micellar rate effect was observed.The SDS-induced selectivity is explained in terms of the micelle-favoring acyclic conformers of linalyl acetate.In contrast to linalyl acetate, solvolysis of geranyl acetate (6) in the SDS micelle at pH 2 gives little product selectivity but yields a 7-fold rate effect relative to no SDS controls.This rate effect results in very different product distributions after 90percent completion of the reaction.The observed SDS rate effect for geranyl acetate is compatible with a difference in solvolysis mechanism for linalyl and geranyl acetate.