2-azadiene

Finally, it should be mentioned (Section 4.04.2.1.9) that pyrazole never reacts as an alkene towards a diene or a 1,3-dipole nor as an azadiene towards a dienophile. 

Vapor phase pyrolysis of 2-dimethylaminoazirine (168), on the other hand, proceeds in a similar manner at 340 °C to give substituted azadiene (169) in high yield (7SJA4409). Azadiene (169) has been employed in the construction of heterocyclic rings such as pyridines via a [4-1-2] cycloaddition-elimination sequence. 

With this foundation, Boger communicated the use of 1,2,4-triazines as a dependable, azadiene equivalent for Diels-Alder approaches to substituted pyridines. Electron rich olefin 19, prepared from the corresponding ketone, was allowed to... 

Heterocyclic and acyclic azadiene Diels-Alder reaction in total synthesis of nothapodyine B, alkaloid with antiviral activity 98JHC1003. 

Intramoleeular Diels-Alder reaetions of azadienes 76 afforded 6-eyano-2,3,4,8,9,9n-hexahydropyrido[2,l-Z)][l,3]oxazines 77 (99TL7211,99TL7215). eyelization was earried out smoothly at or below room temperature in... 

In 1996, the first example of the catalytic enantioselective aza Diels-Alder reactions of azadienes using a chiral lanthanide catalyst was reported [4], In this article, successful examples of such catalytic reactions are surveyed. 

Tab. 5.2 Catalytic enantioselective aza Diels-Alder reactions using azadienes...

In the presence of 10 mol% chiral Cu(II) catalyst 25, 2-azadienes 26 reacted with dienophiles 27 to afford the corresponding piperidone derivatives in high yields... 

Tab. 5.13 Catalytic asymmetric aza Diels-Alder reactions of 2-azadienes...

When a cold (-78 °C) solution of the lithium enolate derived from amide 6 is treated successively with a,/ -unsaturated ester 7 and homogeranyl iodide 8, intermediate 9 is produced in 87% yield (see Scheme 2). All of the carbon atoms that will constitute the complex pentacyclic framework of 1 are introduced in this one-pot operation. After some careful experimentation, a three-step reaction sequence was found to be necessary to accomplish the conversion of both the amide and methyl ester functions to aldehyde groups. Thus, a complete reduction of the methyl ester with diisobutylalu-minum hydride (Dibal-H) furnishes hydroxy amide 10 which is then hydrolyzed with potassium hydroxide in aqueous ethanol. After acidification of the saponification mixture, a 1 1 mixture of diastereomeric 5-lactones 11 is obtained in quantitative yield. Under the harsh conditions required to achieve the hydrolysis of the amide in 10, the stereogenic center bearing the benzyloxypropyl side chain epimerized. Nevertheless, this seemingly unfortunate circumstance is ultimately of no consequence because this carbon will eventually become part of the planar azadiene. 

For examples of Diels-Alder reactions involving 2-azadienes, see (a) Boger, D.L. Weinreb, S.M. In Hetero Diels-Alder Methodology in Organic Synthesis, Academic Press San Diego, 1987, p. 255 (b) Boger, D. L. Tetrahedron 1983, 39, 2869. 

Fischer alkenylcarbene complexes undergo cyclopentannulation to alkenyl AT,AT-dimethylhydrazones (1-amino-1-azadienes) to furnish [3C+2S] substituted cyclopentenes in a regio- and diastereoselective way along with minor amounts of [4S+1C] pyrrole derivatives. Enantiopure carbene complexes derived from (-)-8-(2-naphthyl)menthol afford mixtures of trans,trans-cycloipentenes and ds,ds-cyclopentenes with excellent face selectivity [75]. The mechanism proposed for the formation of these cyclopentene derivatives is outlined in Scheme 28. The process is initiated by nucleophilic 1,2-attack of the carbon... 

The reaction of JV,iV-dimethylhydrazones (1-amino-1-azadienes) and alkenylcarbene complexes mainly produces [3C+2S] cyclopentene derivatives (see Sect. 2.6.4.5). However, a minor product in this reaction is a pyrrole derivative which can be considered as derived from a [4S+1C] cycloaddition process [75]. In this case, the reaction is initiated by the nucleophilic 1,2-addition of the nitrogen lone pair to the metal-carbon double bond followed by cyclisation and... 

S+3C] Heterocyclisations have been successfully effected starting from 4-amino-l-azadiene derivatives. The cycloaddition of reactive 4-amino-1-aza-1,3-butadienes towards alkenylcarbene complexes goes to completion in THF at a temperature as low as -40 °C to produce substituted 4,5-dihydro-3H-azepines in 52-91% yield [115] (Scheme 66). Monitoring the reaction by NMR allowed various intermediates to be determined and the reaction course outlined in Scheme 66 to be established. This mechanism features the following points in the chemistry of Fischer carbene complexes (i) the reaction is initiated at -78 °C by nucleophilic 1,2-addition and (ii) the key step cyclisation is triggered by a [l,2]-W(CO)5 shift. 

Tungsten alkynyl Fischer carbene complexes are excellent dienophile partners in the classical Diels-Alder reaction with 1-azadienes (see Sect. 2.9.2.1). On the contrary, the chromium-derived complexes exhibit a different behaviour and they react through a [4S+3C] heterocyclisation reaction to furnish azepine derivatives [116] (Scheme 68). The reaction is initiated by a 1,2-addition of the nitrogen lone pair to the carbene carbon followed by a [l,2]-Cr(CO)5 shift-pro-... 

Finally, chromium imine carbenes underwent photoreaction with imines to give azadienes (metathesis) (Eq. 36), with azobenzene to give both metathesis and cycloaddition products (Eq. 37), and with ketones to give oxazolines... 

Diels-Alder reactions of 1-azadienes are less thermodynamically favorable [92] than the all-carbon analogs because of the stronger carbon nitrogen 7r-bond which is broken during the Diels-Alder reaction. 

Reactivity of 1-azadienes 87 and the regioselectivity and stereoselectivity of the cycloadditions with dienophiles 88 are strongly dependent on the type of... 

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