Secondary deuterium isotope effects on a cyclic allylic rearrangement

Combining a Clostridial Enzyme Exhibiting Unusual Active Site Plasticity with a Remarkably Facile Sigmatropic Rearrangement: Rapid, Stereocontrolled Entry into Densely Functionalized Fluorinated Phosphonates for Chemical Biology

“…); (v) allylic thionobenzoate rearrangement (−10 e.u.). 55 Prior to these findings, we are aware of only a couple of cases in which a favorable entropy of activation has been observed for a neutral [3,3]-sigmatropic rearrangement in the absence of a catalyst, the most notable involving a system in which a the terminal alkene is masked as a cyclopropane, 54 i.e. technically not a bonafide example of a [3,3]-sigmatropic rearrangement.…”

The Transition State of Free Radical SH2′ Reaction of Allyl Chloride with Organomercurial Study by Inverse Secondary α‐Deuterium Kinetic Isotope Effect

“…1-d-3-Chloro-1-propene (1b) was prepared by chlorination 24 from 3-d-allyl alcohol, which was synthesized by the methods reported in the literature. 25 Phosphorus trichloride (7.8 mL) was added dropwise to the dry DMF (150 mL) under a nitrogen atmosphere in an ice bath with stirring for 1 hr. 3-d-Allyl alcohol (10 mL) was added dropwise to the solution of PCl 3 and DMF in an ice bath.…”

“…The product was isolated by distillation from the crude product. 1 H NMR of compound 1b 26 25 Propargyl alcohol (8.6 mL) was added dropwise under a nitrogen atmosphere to a slurry of lithium aluminum hydride (5.7 g, 0.15 mole) in 150 mL of dry ether with stirring in an ice bath. After the addition was completed (85 min), the reaction mixture was stirred at 0°C for 1 hr, then, the solution was stirred for 24 hrs at room temperature.…”

“…1 Preparation of 1,1-d 2 -3-chloro-1-propene (1c) 1,1-d 2 -3-chloro-1-propene (1c) was synthesized by the same method as compound (1b), that is, compound (1c) was obtained by the chlorination 24 from 3,3-d 2 -allyl alcohol, which was prepared by the methods reported in the literature. 25 25 The synthesis of 3,3-d 2 -allyl alcohol is the same as that of 3-d-allyl alcohol. However, 3-d-propargyl alcohol was used instead of propargyl alcohol.…”

“…1 (14), 56 (13), 55 (17), 53 (6). 25 Propargyl alcohol (11.2 g, 0.20 mole) was equilibrated with 20 g of D 2 O containing 6 mg of barium oxide overnight. The mixture was continuously extracted with 15 mL of ether for 6 hrs, and the ether layer was stirred overnight with 20 g of fresh D 2 O containing 35 mg of BaO.…”