61247-78-7Relevant academic research and scientific papers
Kinetic resolution of unsaturated amides in a chlorocyclization reaction: Concomitant enantiomer differentiation and face selective alkene chlorination by a single catalyst
Jaganathan, Arvind,Staples, Richard J.,Borhan, Babak
, p. 14806 - 14813 (2013/10/22)
The first example of a kinetic resolution via chlorofunctionalization of olefins is reported. The enantiomers of racemic unsaturated amides were found to have different hydrogen-bonding affinities for chiral Lewis bases in numerous solvents. This interaction was exploited in developing a kinetic resolution of racemic unsaturated amides via halocyclization. The same catalyst serves to both sense chirality in the substrate as well as mediate a highly face-selective chlorine delivery onto the olefin functionality, resulting in stereotriad products in up to 99:1 dr and up to 98.5:1.5 er. The selectivity factors were typically greater than 50 to allow for the simultaneous synthesis of both the products and unreacted substrates in highly enantioenriched form at yields approaching 50%. The reaction employs catalytic amounts (≤0.50 mol %) of a commercially available and recyclable organocatalyst.
A dual-catalysis/anion-binding approach to the kinetic resolution of allylic amines
Klauber, Eric G.,Mittal, Nisha,Shah, Tejas K.,Seidel, Daniel
, p. 2464 - 2467 (2011/07/09)
Chemical equations presented. A dual-catalysis approach enables the small-molecule catalyzed kinetic resolution of allylic amines by acylation. By employing 2 mol % of each 4-(pyrrolidino)pyridine (PPY) and a readily available chiral hydrogen-bonding coca
An efficient FeCl3-catalyzed amidation reaction of secondary benzylic and allylic alcohols with carboxamides or p-toluenesulfonamide
Jana, Umasish,Maiti, Sukhendu,Biswas, Srijit
, p. 858 - 862 (2008/04/13)
A simple, inexpensive, environmentally friendly and high yielding amidation reaction of benzylic and allylic alcohols with primary amides using a catalytic amount of FeCl3 (5 mol %) is described. Direct substitution of various amides such as be
Three-component synthesis of amine derivatives using benzylic and allylic alcohols as N-alkylating agents in the absence of external catalysts and additives
Li, Hai-Hua,Dong, De-Jun,Tian, Shi-Kai
experimental part, p. 3623 - 3626 (2009/05/07)
The direct employment of benzylic and allylic alcohols as N-alkylating agents provides a useful synthetic route for amine derivatives by avoiding the preactivation of the hydroxy groups of alcohols. Herein we report a novel by-product-catalyzed three-comp
WITTIG OLEFINATION IN THE ABSENCE OF AN EXOGENOUS BASE: A NEW SYNTHESIS OF α-SUBSTITUTED PRIMARY ALLYLIC AMINES
Dellaria, Joseph F.,Sallin, Kevin J.
, p. 2661 - 2664 (2007/10/02)
A new synthesis of α-substituted primary allylic amines through the in situ generation and trapping of an ylide from the reaction of an N-acyl aziridine, triphenylphosphine, and an aldehyde in refluxing isopropanol is reported.These compounds can be prepared enantioselectively (> 94.6percent ee) by employing a chiral nonracemic N-acyl aziridine.
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.
194. Diastereoselecktive Alkylation of 3-Aminobutanoic Acid in the 2-Position
Estermann, Heinrich,Seebach, Dieter
, p. 1824 - 1840 (2007/10/02)
The enantiomerically pure 3-aminobutanoic acids (R)- and (S)-6 are readily available by preparative HPLC separation of the two diastereoisomers 5 obtained from addition of (S)-phenethylamine to methyl crotonate and subsequent hydrogenolysis (Scheme 2). (S)-methyl 3-(benzoylamino)butanoate ((S)-3) is also available by enzymatic kinetic resolution with pig-liver esterase.The N-benzoyl- and N-benzyloxycarbonyl derivatives rac-3, 8,and 9 of 3-aminobutanoates are doubly deprotonated with LDA and alkylated or aminated in high selectivity (17 examples, relative topicity like; see Tables 1 and 2).The configuration of three of the products is assigned (Schemes 4-6), and in four cases, the free α-substituted β-amino acid is prepared by acidic hydrolysis (see Table 3).It is shown that the doubly lithiated β-amino-acid derivative is solubilized, and its reactivity may be strongly influenced by the presence of 3 equiv. of LiCl.
α-ALKYLATION OF β-AMINOBUTANOATES WITH lk-1,2-INDUCTION
Seebach, Dieter,Estermann, Heinrich
, p. 3103 - 3106 (2007/10/02)
Dilithiated methyl- or ethyl-N-benzoyl-3-aminobutanoates are alkylated or added to benzaldehyde to give products of l- and u,u-configuration respectively.Several methods are presented by which enantiomerically pure 3-aminobutanoic derivatives can be prepared.
