Regioselective biocatalytic self-sufficient Tishchenko-type reaction via formal intramolecular hydride transfer

Abstract

Alcohol dehydrogenases catalyze the regioselective lactonization of dialdehydes via a bio-Tishchenko-like reaction. The nicotinamide-dependent self-sufficient reduction–oxidation sequence proceeds through a formal intramolecular hydride shift.

Alcohol Dehydrogenases as Catalysts in Organic Synthesis

“…Hall and coworkers reported an ADH-catalysed, overall redox-neutral cascade reaction transforming dialdehydes into lactones (Tishchenko-type reaction, Figure 19) (Tassano et al, 2020).…”

Exciting progress in the transition metal‐catalyzed synthesis of oxepines, benzoxepines, dibenzoxepines, and other derivatives

“…In 2020, Tassano et al reported an aqueous sequential chemoenzymatic one‐pot cascade of the palladium‐catalyzed Suzuki–Miyaura coupling and regioselective alcohol dehydrogenase (ADH)‐catalyzed lactonization to provide substituted dibenzo[ c , e ]oxepin‐5(7 H )‐ones 63 . [ 26 ] [1,1′‐Biphenyl]‐2,2′‐dicarbaldehyde substrate 62 was obtained through the cross‐coupling reaction of 2‐bromobenzaldehyde 47 with 2‐formylphenylbronic acids 61 and then intramolecular Tishchenko‐like reaction catalyzed by alcohol dehydrogenase to afford lactone‐type product (Scheme 18).…”

“…The number of biological properties of these compounds is containing anti‐inflammatory, [ 7–9 ] antiproliferative, [ 10 ] antitumor [ 1 ] and anticancer, [ 10 ] antiplasmodial, [ 11 ] antihelminthic activity, [ 12 ] antibiotic activity, [ 13–16 ] antiestrogenic, [ 17 ] analgesic, [ 18 ] antipsychotic, [ 9,19–21 ] angiotensin II receptor antagonistic, [ 22 ] antioxidant, [ 23 ] antimycobacterial, [ 24 ] and antiapoptosis. [ 25 ] Some of oxepine, benzoxepine, and dibenzoxepine derivatives have been synthesized by Tishchenko‐like reaction, [ 26 ] Friedel–Crafts acylation reactions, [ 27 ] Suzuki coupling, [ 28 ] and Catellani reaction. [ 29 ] Transition metal‐catalyzed reactions are powerful tools for the synthesis of useful heterocyclic products from simple and readily available reactants and have received widespread attention due to its high atomic economy.…”

n-Butyllithium-Induced Tandem [3,3]-Sigmatropic Rearrangement and Carbonyl Olefination of Allyl-1,1-dichlorovinyl Ethers

“…Distilled water was used in all experiments. Organic extracts were dried over anhydrous Na 2 SO 4 , filtered, and concentrated in vacuo (20)(21)(22)(23)(24)(25)(26)(27)(28)(29)(30). Chromatography refers to silica gel chromatography (silica gel 60, 230−400 mesh).…”

“…The sixmembered 2-cycloalken-1-ol 4c (entry 8) could be prepared analogously in 56% yield from 1f and the corresponding dione. 21 Finally, combining the ynolate intermediate derived from 1f with 2-(2-oxoethyl) benzaldehyde 22 gave naphthalene 4d in 61% yield after dehydration of the crude decarboxylation product in Ac 2 O at 85 °C for 3 h. 12,13 Utilizing the carbohydrate-derived ynol ether 5a, 4a this method may be applied to the stereoselective synthesis of Cvinyl-Δ 2,3 -glycosides (Scheme 2a). 14−17 Thus, exposure of 5a to 2.2 equiv of n-BuLi at −78 °C for 45 min, followed by acetone addition and reaction quench, gave a crude β-lactone, which was decarboxylated by heating in cyclohexane with silica gel for 1 h to provide the β-vinyl glycoside 6a in 79% yield.…”