85669-64-3Relevant academic research and scientific papers
Copper-Catalyzed Perfluoroalkylation of Allyl Phosphates with Stable Perfluoroalkylzinc Reagents
Liu, Lihua,Bao, Xifei,Xiao, Hua,Li, Junlan,Ye, Feifan,Wang, Chaoqin,Cai, Qinhua,Fan, Shilu
, p. 423 - 434 (2019/01/08)
A general and practical method for copper-catalyzed cross-coupling of allyl phosphates with stable perfluoroalkylzinc reagents has been developed. The reaction proceeds under mild reaction conditions with high efficiency, good functional group tolerance, and high regio- A nd stereoselectivities and provides general, straightforward, and useful access to allyl-perfluoroalkyl compounds. Preliminary mechanistic studies reveal that the allyl copper intermediate may be involved in the catalytic cycle.
Tandem Palladium and Isothiourea Relay Catalysis: Enantioselective Synthesis of α-Amino Acid Derivatives via Allylic Amination and [2,3]-Sigmatropic Rearrangement
Spoehrle, Stéphanie S. M.,West, Thomas H.,Taylor, James E.,Slawin, Alexandra M. Z.,Smith, Andrew D.
supporting information, p. 11895 - 11902 (2017/09/07)
A tandem relay catalytic protocol using both Pd and isothiourea catalysis has been developed for the enantioselective synthesis of α-amino acid derivatives containing two stereogenic centers from readily accessible N,N-disubstituted glycine aryl esters and allylic phosphates. The optimized process uses a bench-stable succinimide-based Pd precatalyst (FurCat) to promote Pd-catalyzed allylic ammonium salt generation from the allylic phosphate and the glycine aryl ester. Subsequent in situ enantioselective [2,3]-sigmatropic rearrangement catalyzed by the isothiourea benzotetramisole forms syn-α-amino acid derivatives with high diastereo- and enantioselectivity. This methodology is most effective using 4-nitrophenylglycine esters and tolerates a variety of substituted cinnamic and styrenyl allylic ethyl phosphates. The use of challenging unsymmetrical N-allyl-N-methylglycine esters is also tolerated under the catalytic relay conditions without compromising stereoselectivity.
Asymmetric synthesis of α-chiral allylic silanes by enantioconvergent γ-selective copper(I)-catalyzed Allylic Silylation
Delvos, Lukas B.,Vyas, Devendra J.,Oestreich, Martin
supporting information, p. 4650 - 4653 (2013/06/05)
Gamma way: Regio- and enantioselective allylic substitution with a silicon nucleophile generated by copper(I)-catalyzed Si-B bond activation provides direct access to α-chiral allylic silanes from linear acceptors. The enantioconvergent catalysis employing McQuade's six-membered N-heterocyclic-carbene-copper(I) catalyst is applicable to aryl- and alkyl-substituted allylic phosphates (see scheme). Copyright
Palladium(0)-Catalyzed Azidation of Allyl Esters. Selective Synthesis of Allyl Azides, Primary Allylamines, and Related Compounds
Murahashi, Shun-Ichi,Taniguchi, Yuki,Imada, Yasushi,Tanigawa, Yoshio
, p. 3292 - 3303 (2007/10/02)
Palladium(0)-catalyzed reaction of allyl esters such as phosphates, carbonates, and carboxylates with sodium azide gives allyl azides.The azidation proceeds with retention of configuration at the allylic carbon.Optically active (R)-(E)-(+)-4-phenyl-3-buten-2-yl azide (19) is obtained from (R)-(E)-(+)-4-phenyl-3-buten-2-yl acetate (18) stereoselectively.Sequential substitution of (Z)-4-acetoxy-2-buten-1-yl diethyl phosphate (24) with nucleophiles and subsequently azide ion gives (E)-4-substituted-2-buten-1-yl azides 27.The reaction of allyl azides with triphenylphosphine gives iminotriphenylphosphoranes, which are versatile synthetic intermediates of primary allylamines, N-allylamines, and N-allylamides.Treatment of allyl azides with triphenylphosphine and subsequently with aqueous ammonium solution gives primary allylamines.Other synthetic applications of allyl azides are also described.
