1- quinolines, reaction with acrylates

Pyrazo[l,5-a]quinolines were synthesized by reaction of acrylates with 1-(Af-methylamino)quinolines 430 to afford the corresponding Michael addition product 431 which upon dehydrogenation with DDQ gave 432. 

Aryl halides which are rather inert in usual organic reactions can undergo reactions by means of palladium catalysts. Thus, styrene and stilbene derivatives are obtained by reaction of olefins with aryl bromides at 125 °C using Pd(0Ac)2 (1 mol%) and tri-(o-tolyl)phosphine (2 mol%)83. The palladium-catalyzed vinylic substitution reaction is applicable to a variety of heterocyclic bromides including pyridine, thiophene, indole, furan, quinoline and isoquinoline84. Thus, reaction of 3-bromopyri-dine with l-(3-butenyl)phthalimide at 100 °C gives l-[4-(3 -pyridyl)-3-butenyl]-phthalimide (yield of mixed amine 57%, selectivity 68%) at 100 °C. This phthalimide is subsequently converted to nornicotine (188) (Scheme 59). The reaction of acrylic... 

Reaction of 2,3-dihydro-3-hydroxy-3-methyl- 240 (R = Me), or a mixture of 2,3-dihydro-3-hydroxy-3-aryl-57/-pyrido[l,2,3-dfe]-l,4-benzoxazin-5-ones 240 (R = Ar) and (8-aroylmethoxy)quinolin-2(l//)-ones 241 (R = Ar) with ethyl 2-(bromomethyl)acrylate in the presence of activated Zn and hydroquinone gave 8-[(2,3,4,5-tetrahydro-4-methylidene-5-oxo-2-furanyl)-methoxy]quinolin-2(l//)-ones (242) (97HCA1161). 6,7-Dihydro derivatives of 240 reacted similarly (00HCA349). 

General procedure for Heck coupling. A mixture of POPd (16.0 mg, 6 mol%), quinoline derivative (0.56 mmol), tert-butyl acrylate (356 mg, 2.8 mmol), and base (0.61 mmol) was stirred in 5 mL of anhydrous DMF at 135 °C for 24 h. The reaction mixture was allowed to cool to room temperature, quenched with water, and extracted with Et20. The combined organic layers were washed with water, dried over MgS04, and the solvents were removed under vacuum. The crude products were purified by flash chromatography on silica gel. 

The mechanisms of aminolysis of substituted phenyl quinoline-8- and -6-carboxylates, (36) and (37), have been evaluated using AMI semiempirical and HF/6-31- -G(d) ab initio quanmm mechanical methods to study the ammonolyses of the model systems vinyl c/x-3-(methyleneamino)acrylate (38), c/x-2-hydroxyvinyl di-3-(methyleneamino)acrylate (39) and vinyl rranx-3-(methyleneamino)acrylate (40). Both experimental and computational results support the formation of a tetrahedral intermediate in the reaction. The results of this study are fully consistent with the experimental observations for the aminolyses of variously substituted phenyl quinoline-8- (36) and -6-carboxylates (37). ... 

Reaction of 2-aminoquinoline either with ethyl 3-chloropropionate for 1 h at 100°C (63YZ682) or with methyl acrylate in the presence of acetic anhydride for 8 h at 120°C (71KGS482) gave 2,3-dihydro-l//-pyrimido[l,2-a]quinolin-3-one (58). 

Diels-Alder Reactions. Bp3-OEt2 is used to catalyze and reverse the regiospecificity of some Diels-Alder reactions, e.g. with pen-hydroxylated naphthoquinones, sulfur-containing conpounds, the reaction of 1-substituted trans-1,3-dienes with 2,6-dimethylbenzoquinones, and the reaction of 6-inethoxy-l-vinyl-3,4-dihydronaphthalene with p-quinones. BFs-OEta has a drastic effect on the regioselectivity of the Diels-Alder reaction of quinoline- and isoquinoline-5,8-dione with piperylene, which produces substituted azaanthraquinones. This Lewis acid is the most effective catalyst for the Diels-Alder reaction of furan with methyl acrylate, giving high endo selectivity in the 7-oxabicyclo[2.2.1]heptene product (eq 35). ... 

Studies on the use of complexes immobilized on quinoline-carboimine-functionalized FSM-16 mesoporous silica for Mizoroki-Heck-type reactions between methyl acrylate (1) and various aryl iodides highlighted the superior catalytic activity of a mthenium(III) catalyst compared with the corresponding platinum(IV) complex [44]. 

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