102024-45-3Relevant academic research and scientific papers
One-Pot Substitution of Aliphatic Alcohols Mediated by Sulfuryl Fluoride
Dubois, Rudy,Epifanov, Maxim,Hodgson, Jack W.,Mo, Jia Yi,Sammis, Glenn M.
, p. 4958 - 4962 (2020)
The Mitsunobu reaction is a powerful transformation for the one-pot activation and substitution of aliphatic alcohols. Significant efforts have focused on modifying the classic conditions to overcome problems associated with purification from phosphine-based byproducts. Herein, we report a phosphine free method for alcohol activation and substitution that is mediated by sulfuryl fluoride. This new method is effective for a wide range of primary alcohols using phthalimide, di-tert-butyl-iminodicarboxylate, and aromatic thiol nucleophiles in 74 % average yield. Activated carbon nucleophiles and a deactivated phenol were also effective for this reaction in good yields. Secondary alcohols were also successful substrates using aryl thiols, affording the corresponding sulfides in 56 % average yield with enantiomeric ratios up to 99:1. This new protocol has a distinct synthetic advantage over many existing phosphine-based methods as the byproducts are readily separable. This feature was exploited in several examples that did not require chromatography for purification. Furthermore, the mild reaction conditions enabled further in situ derivatization for the one-pot conversion of alcohols to amines or sulfones. This method also provides a boarder nucleophile scope compared to existing phosphine-free methods.
A RADICAL DEOXIGENATION OF SECONDARY ALCOHOLS TO HYDROCARBONS BY USE OF TRIBUTYLTIN HYDRIDE
Watanabe, Yoshihiko,Araki, Takumi,Ueno, Yoshio,Endo, Takeshi
, p. 5385 - 5388 (2007/10/02)
Secondary alcohols 1 reacted with 2,2'-dibenzothiazolyldisulfide in the presence of tributylphosphine to give corresponding sulfides 2 in good yields.Sulfides 2 were subsequently desulfurized to hydrocarbons 3 with tributyltin hydride in radical conditions.
