95896-89-2Relevant academic research and scientific papers
One-Pot Synthesis of Homoallylic Alcohols via a Facile Conversion of Allylic Alcohols into Allylic Iodides
Kanai, Takaya,Irifune, Shinji,Ishii, Yasutaka,Ogawa, Masaya
, p. 283 - 286 (1989)
Allylic alcohols were readily converted into allylic iodides by hydrogen iodide generated in situ from chlorotrimethylsilane/sodium iodide and water, or alcohols, under mild conditions.Displacement of allylic alcahols containing a terminal double bond gave allylic iodides accomponied by allylic rearrangement.This procedure has successfully been extended to a one-pot synthesis of homoallylic alcohols by carrying out successive Barbier type reactions.
Mechanistic Studies on a Cu-Catalyzed Asymmetric Allylic Alkylation with Cyclic Racemic Starting Materials
Rideau, Emeline,You, Hengzhi,Sidera, Mireia,Claridge, Timothy D. W.,Fletcher, Stephen P.
, p. 5614 - 5624 (2017/04/27)
Mechanistic studies on Cu-catalyzed asymmetric additions of alkylzirconocene nucleophiles to racemic allylic halide electrophiles were conducted using a combination of isotopic labeling, NMR spectroscopy, kinetic modeling, structure-activity relationships, and new reaction development. Kinetic and dynamic NMR spectroscopic studies provided insight into the oligomeric Cu-ligand complexes, which evolve during the course of the reaction to become faster and more highly enantioselective. The Cu-counterions play a role in both selecting different pathways and in racemizing the starting material via formation of an allyl iodide intermediate. We quantify the rate of Cu-catalyzed allyl iodide isomerization and identify a series of conditions under which the formation and racemization of the allyl iodide occurs. We developed reaction conditions where racemic allylic phosphates are suitable substrates using new phosphoramidite ligand D. D also allows highly enantioselective addition to racemic seven-membered-ring allyl chlorides for the first time.1H and2H NMR spectroscopy experiments on reactions using allylic phosphates showed the importance of allyl chloride intermediates, which form either by the action of TMSCl or from an adventitious chloride source. Overall these studies support a mechanism where complex oligomeric catalysts both racemize the starting material and select one enantiomer for a highly enantioselective reaction. It is anticipated that this work will enable extension of copper-catalyzed asymmetric reactions and provide understanding on how to develop dynamic kinetic asymmetric transformations more broadly.
New halogenation reagent system for one-pot conversion of alcohols into iodides and azides
Kamal, Ahmed,Ramesh,Laxman
, p. 827 - 833 (2007/10/03)
In Situ generation of hydrogen iodide from methanesulphonic acid/sodium iodide in different solvents was found to be an attractive reagent system for the chemoselective conversion of various alcohols to their corresponding iodides. Moreover, treatment of benzylic and allylic alcohols with this reagent system, followed by substitution with azide ion, produced the corresponding azides in one pot in good yields.
The thermal desulfination of allylic sulfonyl halides
King, Malcolm D.,Sue, Rodney E.,White, Rodney H.,Young, David J.
, p. 4493 - 4496 (2007/10/03)
Allylic sulfonyl halides can be generated by halogenolysis of the corresponding triorganotin sulfinates. Allylic sulfonyl bromides and iodides undergo a first order, thermal desulfination with allylic rearrangement to yield the corresponding allylic halides. The desulfination of a cyclic allylic sulfonyl bromide is stereospecific, proceeding with γ-syn bromine migration.
