Synthesis of Epoxides by Palladium-Catalyzed Reactions of Tertiary Allyl Alcohols with Aryl or Alkenyl Halides

Abstract

A novel synthetic method for the preparation of tri- or tetrasubstituted epoxides is reported. Treatment of readily available tertiary allyl alcohol with aryl or alkenyl halide under palladium catalysis resulted in arylative cyclization to form the epoxide. The reaction includes intramolecular C-O bond and intermolecular C-C bond construction.

Copper‐Catalyzed Cyanomethylation of Allylic Alcohols with Concomitant 1,2‐Aryl Migration: Efficient Synthesis of Functionalized Ketones Containing an α‐Quaternary Center

“…Although alkylation-induced 1,2-aryl migration has recently been reported for the conversion of allylic alcohols into ketones, [13] examples of the generation of homologated ketones with the creation of an a-quaternary center are rare. Although the usefulness of the formation of epoxide 3 a is evident, [14] we focused our attention on ketone 2 in this study. When we applied our previously developed alkylative lactonization conditions [Cu(OTf) 2 (2.0 equiv), BiPy (1.0 equiv), DTBP (2.0 equiv), K 3 PO 4 (2.0 equiv), H 2 O (11.0 equiv), air, 140 8C, CH 3 CN (0.1m)], ketone 2 a was formed together with epoxide 3 a in 61 % yield in a 1.9 : 1 ratio.…”

C60 as fine fillers to improve poly(phenylene sulfide) electrical conductivity and mechanical property

“…Solvent could help the tangled PPS molecular chain creeping and stretching in 1-chloronaphthalene, which effectively contributes to the well dispersion of C 60 in PPS matrix. Although the alkylation or acylation was an effective functionalization method for fullerene 38, 39 , herein a C 60 -thiol adducts by reacting C 60 with the end group SH of PPS was easier to take place 32 , and the covalent bond formation improved the C 60 -matrix interfacial adhesion 6, 7 . It is general known that the formation of π-π stacking interactions can be characterized through the shift of –CH bond.…”

Palladium-Catalyzed Heterofunctionalization of C-H, C=C and C≡ C Bonds

“…1), carboamination for the total synthesis of a cytotoxic alkaloid (±)-Tylophorine, 26 (eq. Synthesis of threemembered aziridine [78] and epoxide [79] rings can also be achieved, using S-Phos (27) and Ru-Phos (28), respectively (eq. 3) [77].…”