Direct synthesis of β-acyloxy aldehydes from linear allylic esters using O₂ as the sole oxidant

Abstract

A simple and practical preparation of β-O substituted aldehydes directly from linear allylic esters is developed. Using bis(benzonitrile)palladium chloride as the catalyst and O2 as sole oxidant, the tandem isomerization-...

Phototriggered Self-Catalyzed Three-Component Minisci Reaction: A Route to β-C(sp3) Heteroarylated Alcohols/Ethers

“…Alkenes 2e and 2f were not commercially available and prepared following a procedure previously reported in the literature …”

“…Alkenes 2e and 2f were not commercially available and prepared following a procedure previously reported in the literature. 17 General Procedure for the Synthesis of Alkenes 2e and 2f. To a solution of alcohol (10.0 mmol, 1.0 equiv), DCC (15.0 mmol, 1.5 equiv), and DMAP (3.0 mmol, 30 mol %) in CH 2 Cl 2 (30 mL) was added the acid.…”

TBN as Organic Redox Cocatalyst for Oxidative Tiffeneau–Demjanov-Type Rearrangement Using O2 as Sole Oxidant

“…In our earlier report in Pd-TBN cocatalyzed Wacker oxidation, tert -butanol is essential for achieving aldehyde selectivity, whereas the combination of ethanol and water is important for ketone selectivity . To our surpise, when 1a was treated with 5 mol % of Pd(PhCN) 2 Cl 2 , 10 mol % of TBN, and 5 equiv of H 2 O in t BuOH at room temperature under oxygen atmosphere for 5 h, complete consumption of 1a was observed affording 90% of ring-expansion product 2a and 10% of aldehyde 3a (Entry 5).…”

Preparation and Carbocupration–Silylation of Allyl Propiolates: Vicinal Functionalization To Form Polysubstituted (E)-Vinylic Silanes

“…[15][16][17] Those products were subjected to subsequent transformations including a tandem conjugate addition-diastereoselective protonation sequence, 18 -and halogenations, 19,20 and a stereoselective cascade deconjugation-aldol addition-stabilized Peterson olefination. 21 Re-placement of ethyl esters with O-allylic esters would introduce an additional synthetic handle for Wacker-type oxidations, 22,23 and facile olefin cross or ring-closing metathesis 24,25 and numerous alkene functionalization reactions (Scheme 1).…”