Asymmetric Synthesis of Tetrahydroquinolines through a [3+2] Cycloaddition Controlled by Dienamine Catalysis

Li, Wenjun; Jia, Wei; Jia, Qianfa; Du, Zhiyun; Zhang, Kun; Wang, Jian

doi:10.1002/chem.201402089

Cited by 57 publications

(31 citation statements)

References 52 publications

(28 reference statements)

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“…In the presence of pyrrolidine‐type organocatalysts 6 , the enantioselective [3+2] dipolar cycloaddition reactions of C,N‐cyclic azomethine imines as dipoles with α,β‐unsaturated aldehydes as dipolarophiles could proceed in two different directions. This dual‐reactivity was independently reported by two research groups in 2014 . Du, Wang and co‐workers used β‐arylmethylenals 110 as substrates in the synthesis of new pyrazole derivatives.…”

Section: Pyrazoles Pyrazolines and Pyrazolidinesmentioning

confidence: 59%

“…The generality of the reaction was evaluated for 17 substrates. However, aliphatic enals 113 gave different [3+2] cycloadducts ( 114 ), as shown in Scheme , Equation (2) . In the authors′ opinion, their formation proceeded through α,β‐unsaturated iminium ion A , which played a key role in triggering the normal‐electron‐demand 1,3‐dipolar cycloaddition reaction.…”

Section: Pyrazoles Pyrazolines and Pyrazolidinesmentioning

confidence: 97%

“…Du, Wang and co‐workers used β‐arylmethylenals 110 as substrates in the synthesis of new pyrazole derivatives. The structure of enals 110 allowed them to undergo the inverse‐electron‐demand 1,3‐dipolar cycloaddition of C,N‐cyclic azomethine imines 111 , which proceeded through dienamine catalysis, as shown in Scheme , Equation (1) . Of the four catalysts tested, catalyst 6 was the most successful.…”

Section: Pyrazoles Pyrazolines and Pyrazolidinesmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis of Diheteroatomic Five‐Membered Heterocyclic Compounds from α,β‐Unsaturated Aldehydes

Keiko

Вчисло

2016

Asian J Org Chem

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The recent increasei ni nterest in the chemistry of azoles has been owing to their paramount importance in several essential fields of research, such as pharmacology, medicine, biology, the organic synthesis of fine chemicals, agriculturalc hemistry, and the chemical industry.T his Focus Review summarizes and highlights recently developed methods for the synthesis of five-membered N,N-, N,O-, andN ,Sheterocycles based on the transformations of 2-alkenals. Over the last 15 years, these reactions, which often differ from reactions involving other a,b-unsaturatedc arbonyl compoundsi nt erms of methoda nd results, have gathered significant momentum. The multitude of catalytic and tech-nological novelties discussed in this Focus Review,s uch as asymmetricm etal-and organocatalysis,o ne-pot multicomponent reactions that proceed through domino, cascade, or tandem sequences, and microwave activation,p romote the formation of ad iverse range of target products, the structures of which becomec lear from the mechanistic schemes given in this Focus Review.T he mechanisms discussed reflect great advances in the chemo-, regio-, and stereoselectivity of the reactions of 2-alkenals, which allows new azoles and related compounds (imidazoles, pyrazoles, oxazoles, thiazoles, and their hydrogenatedd erivatives) to be synthesized.[a] Prof.The ORCID identification number(s) for the author(s) of this articlecan be found under http://dx.Scheme2.One-potsynthesis of imidazoles 8 and tentativemechanism of the reaction.T s= 4-toluenesulfonyl, TMS = tert-butyltrimethylsilyl, Bn = benzyl, Lg = leaving group.Scheme3.Enantioselective synthesiso f3-hydroxyalkyl and 3-aminoalkyli midazo[1,2-a]pyridines (9)through an asymmetricorganocatalytic [3+ +2] annulation strategy.Alk = alkyl.Scheme4.One-potsynthesis of imidazole-containingc ondensed heterocycles by the reaction of 2-alkoxypropenalswith N-binucleophiles.Scheme9.Aroute to 2-(1'-alkoxyvinyl)imidazolidines 27 through the condensation of alkoxy propenals.

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Section: Pyrazoles Pyrazolines and Pyrazolidinesmentioning

confidence: 59%

Section: Pyrazoles Pyrazolines and Pyrazolidinesmentioning

confidence: 97%

Section: Pyrazoles Pyrazolines and Pyrazolidinesmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of Diheteroatomic Five‐Membered Heterocyclic Compounds from α,β‐Unsaturated Aldehydes

Keiko

Вчисло

2016

Asian J Org Chem

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“…In the latter case, the reaction proceeds via 3,4-reactivity of the iminium ion reactive intermediates. Products 119 were formed in 79–83% yields, dr > 25:1 and 80–94% ee ( Scheme 36 ) [ 60 ].…”

Section: Synthesis Of Pyrazolidinesmentioning

confidence: 99%

Synthesis of Non-Racemic Pyrazolines and Pyrazolidines by [3+2] Cycloadditions of Azomethine Imines

et al. 2017

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Asymmetric [3+2] cycloadditions of azomethine imines comprise a useful synthetic tool for the construction of pyrazole derivatives with a variable degree of saturation and up to three stereogenic centers. As analogues of pyrrolidines and imidazolidines that are abundant among natural products, pyrazoline and pyrazolidine derivatives represent attractive synthetic targets due to their extensive applications in the chemical and medicinal industries. Following the increased understanding of the mechanistic aspect of metal-catalyzed and organocatalyzed [3+2] cycloadditions of 1,3-dipoles gained over recent years, significant strides have been taken to design and develop new protocols that proceed efficiently under mild synthetic conditions and duly benefit from superior functional group tolerance and selectivity. In this review, we represent the current state of the art in this field and detailed methods for the synthesis of non-racemic pyrazolines and pyrazolidines via [3+2] metal and organocatalyzed transformations reported since the seminal work of Kobayashi et al. and Fu et al. in 2002 and 2003 up to the end of year 2017.

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“…[14] The pioneering contributions during the past decade have led to the discovery of various highly enantioselective a-, b-, gfunctionalizations and cycloaddition reactions of enals. [14][15][16] Inspired by the synthetic potential of dienamine activation, we investigated the recently designed enaldiazo compounds (diazoenals) [17,18] as precursors for novel dienamines.O ur studies revealed that rhodium-catalyzed reactions of enaldiazo carbonyl compounds with secondary arylamines readily furnishes novel g-amino-substituted donor-acceptor dienamines (Scheme 1b). To the best of our knowledge,this is the first report on the formation of functionalized dienamines through carbenoids.…”

mentioning

confidence: 99%

Dienamine Activation of Diazoenals: Application to the Direct Synthesis of Functionalized 1,4‐Oxazines

Kalepu

Katukojvala

2016

Angew Chem Int Ed

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A novel rhodium-catalyzed dienamine activation of diazoenals resulted in a new class of γ-functionalized donor-acceptor dienamines. The synthetic utility of these dienamines has been demonstrated in a cooperative rhodium(II)/Brønsted acid and gold(I)-catalyzed direct [3+3] annulation of enaldiazo ketones with N-propargyl anilines, thus leading to highly substituted enal-functionalized 1,4-oxazines. The reaction is proposed to involve dienamine activation through the diacceptor rhodium enalcarbenoid NH-insertion and a gold-catalyzed intramolecular site-selective 6-exo-dig heterocyclization. The methodology was applied to the efficient synthesis of structurally complex [1,4]oxazino[4,3-a]quinolone, which is present in the antibacterial agent PNU-286607.

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Asymmetric Synthesis of Tetrahydroquinolines through a [3+2] Cycloaddition Controlled by Dienamine Catalysis

Cited by 57 publications

References 52 publications

Synthesis of Diheteroatomic Five‐Membered Heterocyclic Compounds from α,β‐Unsaturated Aldehydes

Synthesis of Diheteroatomic Five‐Membered Heterocyclic Compounds from α,β‐Unsaturated Aldehydes

Synthesis of Non-Racemic Pyrazolines and Pyrazolidines by [3+2] Cycloadditions of Azomethine Imines

Dienamine Activation of Diazoenals: Application to the Direct Synthesis of Functionalized 1,4‐Oxazines

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