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Reactions of Triafulvenes with Cyclic Imines

Reactions of a series of 4-cyano- and 4-acylsubstituted triafulvenes 1-5 wiith cyclic imines 8-13 give rise to polyheterocyclic derivatives of 2-methylenetetrahydropyridine (14, 18, 20, 31, 33), 4-methylene tetrahydroazocines (37) and 4(2)-methylene-2(3)-pyrrolines (41-43).The spectroscopic and chemical properties of the products obtained, as well as their independent syntheses in some cases, are reported.

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Substituted 2-[monoannelated (3,4-,4,5-, and 5,6-) pyridylalkylenesulfinyl]benzimidazoles

The present invention provides novel substituted 2-[monoannelated(3,4- 4,5-, and 5,6-)pyridylalkylenesulfinyl]-benzimidazoles with gastric acid inhibiting effects.

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Synthetic and mechanistic study on the microwave assisted fries rearrangement of 1-methylidene-3,4-dihydroisoquinoline-2(1H)-yl-methanones

Formerly, an unexpected acyl migration of 1-methylidene-3,4-dihydroisoquinoline- 2(1H)-yl-methanone derivatives was observed, and on this basis a microwave assisted synthetic method was developed for the preparation of members of the 2?-(3,4- dihydroisoquinoline-1-ylidene)-1-ethan-1-one family, potential CB2 receptor agonists and PDE7 inhibitors. The reaction mechanism was studied with experimental and theoretical methods in order to propose intra- and intermolecular radical pathways.

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NOVEL FORMATION OF 9,18-DIFORMYL-5,6,14,17-TETRAHYDRO-8,17-EPOXY-6H,15H-<1,5>DIAZOCINO<2,1-a : 6,5-a'>DIISOQUINONES FROM (3,4-DIHYDROISOQUINOLINYL-1)PROPAN-1,3-DIALS

The title compounds 7-10 are formed from the dialdehydes 1 on treatment with acetic anhydride.

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NITROGEN BRIDGEHEAD COMPOUNDS. PART 67. PREPARATION OF NOVEL POLICYCLIC QUATERNARY SALTS

The first representatives of new polycyclic ring systems – thiazolo- and oxazolo-<2,3-b> triazaphenalenes, benzoxazolo- and benzothiazolo-<2,3-b> triazaphenalenes and isoquinolo-<1,2-b>triazaphenalenes – are prepared by the cycloaddition of pyrido<1,2-a>pyrimidine derivatives with cyclic azomethines.

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Efficient syntheses of polyannular heterocycles featuring microwave- accelerated Bischler-Napieralski reaction, stereoselective Heck cyclization, and Claisen rearrangement

We report the synthesis of the polyannular heterocyclic compounds 1-7. The polyannular systems in the target molecules have been obtained using stereoselective Heck reactions of suitable o-substituted iodoarenes. Additionally, the first report on microwave-accelerated Bischler-Napieralski reaction is disclosed, which has been used in the syntheses of heterocycles 1-3. The compound 7, bearing a quaternary stereogenic center, has been prepared through a stereo-controlled Claisen-Johnson rearrangement from a derivative of the allylic alcohol 25.

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Copper-catalyzed condensation of imines and alpha-diazo-beta-dicarbonyl compounds: modular and regiocontrolled synthesis of multisubstituted pyrroles

In the presence of a copper(ii) catalyst, enolizable imines bearing various N-substituents and alpha-diazo-beta-ketoesters undergo denitrogenative and dehydrative condensation to afford highly substituted pyrroles in moderate to good yields with exclusive regioselectivity. The reaction likely involves nucleophilic addition of the imine nitrogen to a copper carbenoid, tautomerization of the resulting azomethine ylide to an alpha-enaminoketone, and a subsequent enamine-ketone cyclocondensation. With Yb(OTf)3 as a unique cocatalyst, alpha-diazo-beta-diketones also participate in the same condensation reaction. The present reaction is applicable to acyclic, exocyclic, and endocyclic imines with tolerance of a broad range of functional groups and heterocyclic moieties, thus opening a new convenient route for the synthesis of the lamellarin family of natural products.

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2-Methylpyridinium Salts as 1,4-Dinucleophiles. II. Westphal Condensation with Substituted Pyridinium Substrates

Condensation of alpha-methylpyridinium, quinolinium and isoquinolinium salts with 1,2-dicarbonyls in the presence of base, yielded quinolizinium derivatives.In an analogous process, alpha-benzyl derivatives produced 2,3-dihydroindolizin-2-ones by intramolecular cyclisation.

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STRUCTURE AND PROPERTIES OF 8-AZASTEROIDS SYNTHESIZED BY REGIO- AND STEREOSELECTIVE ANNELATION OF 3,4-DIHYDROISOQUINOLINES BY ASYMMETRIC 2-ACYL-1,3-CYCLOHEXANEDIONES

It was found that annelation of 3,4-dihydroisoquinolines by 2-acyl-1,3-cyclohexanediones takes place regio- and stereoselectively, leading to C(11)- and C(17)-substituted derivatives of the 8-aza-D-homogonane series with a trans-disposition of the substituents (Me, Br, Cl, COOMe) at the above positions relative to the angular substituent (H, Me) at C(9). It was shown that the C(17)-halogen and methoxycarbonyl derivatives exist in crystals in the form of one stereoisomer, while in solutions as a mixture of stereoisomers, caused by a keto-enol tautomerism of the C(17a)-carbonyl. In solutions of acids, these derivatives exist in N(8)-…-C(17a) immonium-enol form, as one stereoisomer. It was found that the C(11)-methyl derivatives are obtained in the form of two restrained conformers with respect to ring C, which on boiling are reduced to one conformer. The assignment of the enol regiomers of 4-substituted 2-acetyldimedones has been carried out.

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Pivotal role of an endogenous tetrahydroisoquinoline, salsolinol, in stress- and suckling-induced release of prolactin

In mammals, the role of a prolactin-releasing factor (PRF) in the acute changes of prolactin (PRL) secretion that usually occur after challenges (e.g., suckling stimulus or stress) of homeostasis has been suspected for a long time. We have recently observed that 1-methyl-6,7-dihydroxy-1,2,3,4- tetrahydroisoquinoline, salsolinol (SAL), produced by the hypothalamus and the neuro-intermediate lobe (NIL) of the pituitary gland, can selectively release PRL from the anterior lobe (AL). Moreover, binding sites for SAL have been detected in areas like median eminence, NIL, and AL. It has been proposed that SAL is a putative endogenous PRF. We have also found that a structural analogue of SAL, 1-methyl-3,4-dihydroisoquinoline (1MeDIQ), is able to block dose-dependently SAL-,suckling-,and immobilization (IMO) stress-induced release of PRL without having any influence on alpha-methyl-p-tyrosine (alphaMpT)-induced PRL responses. Neither SAL nor 1MeDIQ has any effect on alpha-melanocyte-stimulating hormone (alphaMSH), adrenocorticotrophic hormone (ACTH), beta-endorphin (beta-END) and arginine-vasopressin (AVP) secretion. Moreover, SAL-induced PRL response was attenuated in male rats pretreated with dexamethasone (DEX). These results strongly suggest that SAL has an important role in the regulation of PRL release induced by physiologic and environmental stimuli; therefore, it can be considered as the strongest candidate for being the PRF in the hypothalamo-hypophysial system. Our findings also indicate that the adrenal steroids may play an inhibitory feedback role in SAL-mediated PRL response.

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