87161-56-6Relevant academic research and scientific papers
Reduction of alkyl and vinyl sulfonates using the CuCl2· 2H2O-Li-DTBB(cat.) system
Radivoy, Gabriel,Alonso, Francisco,Moglie, Yanina,Vitale, Cristian,Yus, Miguel
, p. 3859 - 3864 (2007/10/03)
The reduction of a series of alkyl mesylates, dimesylates and triflates to the corresponding hydrocarbons was efficiently performed using a reducing system composed of CuCl2·2H2O, an excess of lithium sand and a catalytic amount (5 mol%) of 4,4′-di-tert-butylbiphenyl (DTBB), in tetrahydrofuran at room temperature. The process was also applied to enol and dienol triflates affording alkenes and dienes, respectively. The use of the deuterated copper salt CuCl2·2D2O allowed the simple preparation of the corresponding deuterated products.
Chloromethanesulfonate as an efficient leaving group: Rearrangement of the carbon-carbon bond and conversion of alcohols into azides and nitriles
Shimizu, Takeshi,Ohzeki, Tomoya,Hiramoto, Katsuya,Hori, Nobuyuki,Nakata, Tadashi
, p. 1373 - 1385 (2007/10/03)
The chloromethanesulfonate (monochlate) served as an efficient leaving group for rearrangement of the carbon-carbon bond and conversion of alcohols into azides and nitriles. The treatment of the monochlate 16a with zinc acetate in dioxane at 90 °C effected migration of the 4α-methyl group to give alkene 17a. Upon similar treatment of the monochlates 22a, 25a, 28a, and 31a with zinc acetate, the carbon-carbon bonds antiperiplanar to the hydroxyl groups efficiently migrated to afford the alkenes 23a, 26a-c, 29a,b, and 32a, respectively. In the case of the diol 40, the monochlate was converted into the ketone 41 via a rearrangement-ring expansion. The reaction of the monochlates 44a, 47a, 49a, 52a, and 57a with sodium azide or lithium azide in N,N-dimethylformamide efficiently afforded the azides with inversion of the configuration. The introduction of a nitrile group to the sterically hindered alcohol 59 was performed in high yield by the reaction of the monochlate 60a with sodium cyanide.
Efficient method for inversion of secondary alcohols by reaction of chloromethanesulfonates with cesium acetate
Shimizu, Takeshi,Hiranuma, Sayoko,Nakata, Tadashi
, p. 6145 - 6148 (2007/10/03)
Inversion of a variety of secondary alcohols using the (chloromethylsulfonyl)oxy group as a favorable leaving group with cesium acetate in the presence of 18-crown-6 has been performed to give the inverted acetates in high yields.
Formation of sulfinate esters in the synthesis of triflates
Netscher, Thomas,Bohrer, Patrick
, p. 8359 - 8362 (2007/10/03)
On standard treatment of sterically congested alcohols and phenols with triflic anhydride in the presence of amines, trifluoromethanesulfinyl esters were unexpectedly found. Depending on the reaction conditions and the structures of both hydroxy compound and base, esterified products (yields 5% to 99%) containing 0% to 89% (!) of sulfinates were obtained. The mechanisms of these reactions are discussed. The results of the present study indicate how to avoid unwanted sulfinate formation in triflate synthesis.
Stereochemistry of Nucleophilic Substitution of Menthyl Derivatives with Anion of Diphenylphosphine Oxide by an Action of Sodium Dihydridobis(2-methoxyethanolato)aluminate
Yamashita, Mitsuji,Soeda, Yukio,Suzuki, Nobuyoshi,Yamada, Manabu,Tsunekawa, Kenji,et al.
, p. 1871 - 1872 (2007/10/02)
The reaction of an anion of diphenylphosphine oxide prepared by the action of sodium dihydridobis(2-methoxyethanolato)aluminate on the oxide with various menthyl or neomenthyl halides and sulfonates were studied to clarify the sterochemistry of the substi
