Tertiary alcohol synthesis from secondary alcohols via C–H insertion

Abstract

Secondary alcohols are converted into 3(2H)-furanone derivatives via C-H insertion reaction, from which tertiary alcohols are prepared with retention of stereochemistry.

Synthesis of the Tetracyclic Bis(acetal) Lactone Portion of Saudin

“…The conversion of the formyl moiety into a formate moiety (6 Ǟ11) was accomplished through a BaeyerϪVilliger oxidation [23] in heterogeneous phase with mCPBA and NaHCO 3 in CH 2 Cl 2 , and the resulting diester 11 was obtained in quantitative yield. This transformation is clearly shown by the 1 H NMR upfield shift of the formyl proton signal from δ ϭ 9.82 to δ ϭ 8.46, a characteristic value for a formate, as well as the 13 C NMR carbonyl shift from δ ϭ 205.78 to δ ϭ 159.86 ppm.…”

100 Years of the Wolff Rearrangement

“…[13] β-Diketones are efficiently converted into 2-diazo-1,3-diketones on exposure to tosyl azide in the presence of a weak base. Although triethylamine in acetonitrile is routinely used, K 2 CO 3 / MeCN, [415] Cs 2 CO 3 /THF, [416] Al 2 O 3 /KF/THF, [417] and KF·2H 2 O/CH 2 Cl 2 [418] were recommended as alternatives. Several sulfonyl azides were found to offer advantages in safety and facility of product separation over tosyl azide, the most popular diazo transfer reagent.…”

Catalytic Hydrogenation using Ionic Liquids as Catalyst Phase

“…Lee et al [103] synthesized a chiral Rh-complex with a bisphosphine-containing cation as ligand ( Fig. 41.8, 2) to improve the immobilization of the transition-metal complex within the ionic liquid.…”

“…12 Rh-catalyzed enantiomeric hydrogenation of Nacetylphenylethenamine using Rh-complex 2 and Me-BDPMI 3 in a [BMIM][SbF 6 ]/iPrOH two-phase solvent systems[103]. a) Determined by NMR and GC.…”