Construction of Tetrahydrofurans by Pd^II/Pd^IV‐Catalyzed Aminooxygenation of Alkenes

Abstract

Resolute in the face of elimination: Substituted 3‐aminotetrahydrofurans were prepared in good yield and with modest to high diastereoselectivity by the Pd‐catalyzed reaction shown in the scheme (Phth=phthaloyl). Mechanistic studies indicate a PdII/PdIV catalytic cycle involving cis aminopalladation and intramolecular CO bond‐forming reductive elimination with retention of configuration at the carbon atom.

High‐Oxidation‐State Palladium Catalysis: New Reactivity for Organic Synthesis

“…[62] Desai and Sanford employed homoallylic alcohols for an inter-/intramolecular aminoalkoxylation reaction with phthalimide as the nitrogen source (Scheme 17 c). [63] These reactions yield 3,4-disubstituted THF products with high anti diastereoselectivity. THF formation from an internal alkene gives a final product with a configuration that suggests an unusual syn-selective reductive elimination from Pd IV (Scheme 17 d); a reductive elimination of this type apparently also occurs in the alkoxylation reactions in Schemes 9 and 13 c.…”

1,2,3‐Trisubstituted Indanes by Highly Diastereoselective Palladium‐Catalyzed Oxyarylation of Indenes with Arylboronic Acids and Nitroxides

“…(1)]. [1] Dioxygenations, [2] diamidations, [3] and oxyamidations [4] have been realized. However, compared to difunctionalization, in which two heteroatom-containing groups are added to the olefin, and even when considering metals other than palladium, there are only very few reports on intermolecular metalmediated oxidative carbofunctionalization of olefins [Eq.…”

Palladium Complex Bearing 3,5-Bis(benzotriazol-1-Ylmethyl)toluene Ligand Catalyzes Oxidative Amination of Allyl Butyl Ether

“…When PhI(OAc) 2 is used (entry 2) there is partial decomposition with formation of palladium metal. PhICl 2 , however was found to be a suitable oxidant 41,42 . The new complex 2 has slightly higher yields than complex 3 under similar conditions (entries 10-13), probably due to the fact that the more extended conjugation of the benzotriazole rings makes the metal center more electron deficient and consequently increases the reactivity.…”