Acryloyl amide

As pointed out above, no selectivity guarantee can be given for the separation on a certain chiral stationary phase. Therefore, screening routines have to be followed to obtain the appropriate adsorbent. The first possibility is the knowledge-based approach. Some CSP exhibit a certain group-specificity, e.g. the quinine-based CSPs for N-derivatized amino acids or the poly-(N-acryloyl amide derivatives) for five-membered... 

This process was also extended to the formation of /3-hydroxylactams from a ,/3-unsaturated amides with tethered keto-amides 249 (Scheme 111) (179-181). Various substrates underwent cyclizations resulting in the corresponding /3-hydroxylactams 250 with high diastereoselectivities (>95 5) and moderate yields (52-70%). The reaction was tolerant of a wide range of ketones including alkyl, aromatic, and heteroaromatic ketones. Substituents on the /3-position of a,p-unsaturated amides were not well tolerated. Acryloyl amides were found to be the best substrates for this type of cyclization. In addition, crotonoyl amide also underwent cyclization, but conversions and reaction rates were diminished. A... 

Indeed, the polymeric interface seems to be highly diffuse and hydrophilic because copolymers of N-vinylpyrrolidone and N- (2-hydroxyethyl) acrylamide are readily soluble in water [53]. Besides, aminopropyl-glass adsorbs the acryloyl chloride copolymer so that only 10% of its active functions become amidated. The rest is located on the loops and tails of the attached macromolecules [51]. Thus the steric repulsion of the bonded phase is a probable reason for the high inertness of the packing towards viruses. 

The highly ordered cyclic TS of the D-A reaction permits design of diastereo-or enantioselective reactions. (See Section 2.4 of Part A to review the principles of diastereoselectivity and enantioselectivity.) One way to achieve this is to install a chiral auxiliary.80 The cycloaddition proceeds to give two diastereomeric products that can be separated and purified. Because of the lower temperature required and the greater stereoselectivity observed in Lewis acid-catalyzed reactions, the best diastereoselectivity is observed in catalyzed reactions. Several chiral auxiliaries that are capable of high levels of diastereoselectivity have been developed. Chiral esters and amides of acrylic acid are particularly useful because the auxiliary can be recovered by hydrolysis of the purified adduct to give the enantiomerically pure carboxylic acid. Early examples involved acryloyl esters of chiral alcohols, including lactates and mandelates. Esters of the lactone of 2,4-dihydroxy-3,3-dimethylbutanoic acid (pantolactone) have also proven useful. 

The scheme used to prepare the direct 8-aza-analogue 21 of estrone bears at least formal similarity to the Torgov-Smith steroid total synthesis sequence. Acylation of the phenethylamine 9 with acryloyl chloride gives amide 16. Michael addition of dimethylamine followed by Bischler-Napieralski cyclodehydration gives the dihydroisoquinoline, 17. 

The first organoaluminium complex that catalysed a Diels Alder reaction was formed from menthol and ethylaluminium dichloride. This finding was complemented by work of Corey who showed that the aluminium diamine complex (49) was effective for controlling the stereochemistry of Diels-Alder reactions involving cyclopentadiene and acryloyl and crotonyl amides (e.g. 

Fig. 18 Suggested reaction mechanism for the construction of pyrrolo[3,4-h]pyridme-5-ones (50) from the MCR between isocyano amides, aldehydes, amines, and acryloyl chloride derivatives...

Kropachev and his co-workers (82) have described a polymeric derivate of sulfanilic amide with a prolonged activity. They prepared copolymers of N-meth-acryloyl-4-aminobenzenesulfamide with N-vinylpyrrolidone [20). 

Acryloyl and crotonoyl amides (9) derived from the sultam (8), available from ( + )-l, are somewhat more reactive dienophiles than the i orresponding esters (3) derived from 2. Diels-Alder reactions of 9 with cyclopentadiene catalyzed by TiCU or C2H,AIC1, proceed in high yield, with high endo selectivity ( 99%) ind diastereoselectivity of —95% de. The chiral auxiliary is removed by reduction witfi LiAIH4 to furnish 8 and the chiral alcohol in 89-95% yield.-... 

Preparation and Stability. Since A -unsubstituted oxazo-lidines are labile to hydrolysis, they should be transformed immediately after preparation to amide derivatives, which show much higher stability. Thus reaction of (S)-3-amino-2-methyl-4-phenyl-2-butanol with acetone in the presence of a catalytic amount of p-Toluenesulfonic Acid produces (S)-4-benzyl-2,2,5,5-tetramethyloxazolidine. A -Acylation using acryloyl, cinnamoyl, and propanoyl chloride (Et3N, —78°C) gives the corresponding amides. The 7V-crotonoyl derivative is better obtained by the crotonoylation of (S)-3-amino-2-methyl-4-phenyl-2-butanol followed by acetalization with (Me)2C(OMe)2. 

Unsaturated Amides. Cycloaddition of (S)-3-acryloyl-4-benzyl-2,2,5,5-tetramethyloxazolidine with Benzonitrile Oxide proceeds smoothly at 0°C to provide the corresponding oxazolidine in a 93 7 diastereomer ratio (eq 1), which is quantitatively reduced with Lithium Triethylborohydride to give the isoxazoline-5-methanol derivative without loss of enantiomeric purity. A single diastereomer of isox-azoline can be obtained when 3-acryloyl-2,2-dimethyl-4-diphenylmethyloxazolidine is employed. ... 

In the 3-(5 -nitro-2 -furyl)acryloyl group XV, activity was poor when Z was pyrazoline, alkyl or carbethoxyalkyl.°l °2 en Z was 2-imidazoline. Staph, activity was lost without change in Coli activity relative to the sin5>le amide J z = VJhen bromine is present (z = CHpBr or NF—CH=... 

Our polymer requires a reaction between a carboxylic acid or amide and a molecule containing a photolabile group. Candidates considered for that molecule included glycldyl methacrylate 1, acryloyl chloride 2, and isocyanotoethyl methacrylate (IEM) 3. ... 

Vinylogous urea substrates have also been used in the aza-annulation reaction to form 6-lactam products. This process was illustrated by the condensation of fi-keto amide 366 followed by aza-annulation with acryloyl chloride to give 367 (eq. 75).57-59 Catalytic reduction of the tetrasubstituted double bond led to stereoselective formation of 368. The products formed in this reaction were fi-enamino peptide units, and this chemistry can be extended to the preparation of tri-and tetrapeptide analogs. 

Phosphonate groups also provided regiochemical control in the aza-annulation reaction. Condensation of 409 with BnNH2, followed by reaction with acryloyl chloride gave 410 in good yield (eq. 83).57 59 Catalytic hydrogenation of 410 was less efficient than the corresponding ester and amide derivatives and resulted in the formation of a mixture of diastereomeric products 411. 

In the case of synthetic elastomers formed by free radical emulsion techniques, monomers that contain both an antioxidant moiety and a polymerizable function can be copolymerized (6). A series of esters and amides containing the 4-anilinophenyl group or the 3,5-di- er -butyl-4-hydroxyphenol group and a polymerizable a, /3-unsaturated acyl group such as acryloyl or methacryloyl were incorporated into the polymer. 

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