21658-35-5Relevant articles and documents
Aromatic Claisen Rearrangements of Benzyl Ketene Acetals: Conversion of Benzylic Alcohols to (ortho-Tolyl)acetates
Burns, Jed M.,Krenske, Elizabeth H.,McGeary, Ross P.
, p. 252 - 256 (2017/01/24)
Claisen rearrangements of benzyl vinyl ethers are much less facile than those of aliphatic allyl vinyl ethers, and their synthetic utility has remained relatively unexplored. A one-pot procedure is reported for the generation and Claisen rearrangement of benzyl vinyl ethers that contain an activating α-alkoxy substituent on the vinyl group. A [3,3]-sigmatropic mechanism was supported by trapping of the intermediate isotoluene in an intramolecular Alder–ene reaction.
Large hydrophobic interactions with clearly defined geometry. A dimeric steroid with catalytic properties.
Guthrie, J. Peter,Cullimore, Patricia A.,McDonald, Robert S.,O'Leary, Stella
, p. 747 - 764 (2007/10/02)
The steroid dimer α,α'-bis(17β-(4'-imidazolyl)-11-keto-5α-androstan-3β-amino)-p-xylene, 3, has been synthesized by reductive amination of 17β-(4'-imidazolyl)-5α-androstane-3,11-dione by p-xylenediamine in the presence of sodium cyanoborohydride, and by reductive amination of terephthalaldehyde by 3β-amino-17β-(4'-imidazolyl)-5α-androstan-11-one.The second method is stereochemically unambiguous; the first is not.Compound 3 acts as a catalyst for the hydrolysis of 3-arylpropionate esters of 3-hydroxy-4-nitrobenzoic acid.For the phenanthryl propionate the rateenhancement relative to imidazole is 200-fold, and the rate enhancement relative to the hypothetical rate for the propionate reacting with the steroid by the same transition state geometry is 3000-fold.The slope of a plot kkorr vs. ? for the reaction of 3b with aryl propionate ester was 0.83; the corresponding slope for 12 was 0.39.This provides a design parameter for the construction of artificial enzymes.