Amine‐Catalyzed Enantioselective 1,3‐Dipolar Cycloadditions of Aldehydes to C,N‐Cyclic Azomethine Imines

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

doi:10.1002/chem.201400333

Cited by 47 publications

(20 citation statements)

References 61 publications

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“…50 Different type of dipolarophiles have been investigated under thermal conditions with azomethine imines 166 derived from unsubstituted 165, among them, acetylenic sulfones, 106 arynes, 107 β-nitrostyrenes, 108 cyclic vinyl sulfones, 109 and trifluoroethylidene malonates. 110 In the case of using azlactones 189 as dipolarophiles, a [3+2] cycloaddition, followed by a rearrangement at room temperature, gave the pyrazolopirazolone derivatives 190 (Scheme 71).…”

Section: Scheme 70 Synthesis Of Polyoxygenated Diazatriquinane 188 VImentioning

confidence: 99%

1,3-Dipolar cycloadditions of azomethine imines

2015

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Azomethine imines are considered 1,3-dipoles of the aza-allyl type which are transient intermediates and should be generated in situ but can also be stable and isolable compounds. They react with electron-rich and electron-poor olefins as well as with acetylenic compounds and allenoates mainly by a [3 + 2] cycloaddition but they can also take part in [3 + 3], [4 + 3], [3 + 2 + 2] and [5 + 3] with different dipolarophiles. These 1,3-dipolar cycloadditions (1,3-DC) can be performed not only under thermal or microwave conditions but also using metallo- and organocatalytic systems. In recent years enantiocatalyzed 1,3-dipolar cycloadditions have been extensively considered and applied to the synthesis of a great variety of dinitrogenated heterocycles with biological activity. Acyclic azomethine imines derived from mono and disubstituted hydrazones could be generated by prototropy under heating or by using Lewis or Brønsted acids to give, after [3 + 2] cycloadditions, pyrazolidines and pyrazolines. Cyclic azomethine imines, incorporating a C-N bond in a ring, such as isoquinolinium imides are the most widely used dipoles in normal and inverse-electron demand 1,3-DC allowing the synthesis of tetrahydro-, dihydro- and unsaturated pyrazolo[1,5-a]isoquinolines in racemic and enantioenriched forms with interesting biological activity. Pyridinium and quinolinium imides give the corresponding pyrazolopyridines and indazolo[3,2-a]isoquinolines, respectively. In the case of cyclic azomethine imines with an N-N bond incorporated into a ring, N-alkylidene-3-oxo-pyrazolidinium ylides are the most popular stable and isolated dipoles able to form dinitrogen-fused saturated and unsaturated pyrazolopyrazolones as racemic or enantiomerically enriched compounds present in many pharmaceuticals, agrochemicals and other useful chemicals.

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Section: Scheme 70 Synthesis Of Polyoxygenated Diazatriquinane 188 VImentioning

confidence: 99%

1,3-Dipolar cycloadditions of azomethine imines

2015

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“…There were, however, many successful predictions. For example, CSD entry QIXHUC (Li et al, 2014) was successfully used as a shape analogue for CSD entry REDNIX (Steiner et al, 1997). Both are Z 0 = 2, Z r = 1 structures in the space group P2 1 containing elongated molecules forming dimers between the crystallographically independent molecules that are related to one another by approximate 2 1 screw axes.…”

Section: Tablementioning

confidence: 99%

Generation of crystal structures using known crystal structures as analogues

Cole

Groom

Read

et al. 2016

Acta Crystallogr B Struct Sci Cryst Eng Mater

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“…Scheme 17 Thiourea-catalyzed IED 1,3-dipolar cycloaddition of C,Ncyclic azomethine imines with azlactones Proline derivatives have also been used as asymmetric organocatalysts in the reaction of aldehydes/ketones with C,N-cyclic methine imines, as one of the strategies for nucleophile activation. In 2014, enantioselective 1,3-dipolar cycloadditions of aldehydes to C,N-cyclic azomethine imines were developed by Wang's group 51 and Alemán's group 52 respectively. Wang and co-workers reported that various substituted C,N-cyclic azomethine imines and aldehydes underwent IED [3+2] cycloaddition smoothly in the…”

Section: Ied [3+2] Cycloaddition Of Cn-cyclic N′-acyl Azomethine Iminesmentioning

confidence: 99%

“…presence of chiral prolinol silyl ether catalyst C14 and gave C 1 -substituted THIQs 40 with high stereoselectivities (Scheme 18a). 51 The formation of an intermediate enamine was the key step to this reaction. Without the addition of acetic acid, no desired cycloaddition adduct was observed.…”

Section: Short Review Synthesismentioning

confidence: 99%

Asymmetric Synthesis of C1-Chiral THIQs with Imines in Isoquinoline Rings

Chen

Gao

2020

Synthesis

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Tetrahydroisoquinoline (THIQ) scaffolds are important structural units that widely exist in a variety of natural alkaloids and synthetic analogues. Asymmetric synthesis of C1-chiral THIQ is of particular importance due to its significant pharmaceutical, agrochemical, and other biological activities, and the usually distinct bioactivities exhibited by the two enantiomers. In this review, we highlight the significant advances achieved in this field, present recent asymmetric synthesis with imines in isoquinoline rings ordered according to the sequence of various substrate types. New strategies could be inspired and more types of substrates need further development.1 Introduction2 Catalytic Asymmetric Reaction of Dihydroisoquinolines2.1 Asymmetric Reactions of 3,4-Dihydroisoquinolines2.2 Asymmetric Reactions of Dihydroisoquinolinium Salts2.3 Asymmetric Reactions of C,N-Cyclic N′-Acyl Azomethine Imines2.3.1 NED [3+2] Cycloaddition of C,N-Cyclic N′-Acyl Azomethine Imines2.3.2 IED [3+2] Cycloaddition of C,N-Cyclic N′-Acyl Azomethine Imines2.3.3 [3+3] Cycloaddition of C,N-Cyclic N′-Acyl Azomethine Imines2.3.4 [4+3] Cycloaddition of C,N-Cyclic N′-Acyl Azomethine Imines2.3.5 Asymmetric Addition Reactions to C,N-Cyclic N′-Acyl Azomethine Imines2.4 Asymmetric Reactions of C,N-Cyclic Nitrones3 Catalytic Asymmetric Mannich Reactions of Isoquinolines4 Conclusions and Perspectives

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Amine‐Catalyzed Enantioselective 1,3‐Dipolar Cycloadditions of Aldehydes to C,N‐Cyclic Azomethine Imines

Cited by 47 publications

References 61 publications

1,3-Dipolar cycloadditions of azomethine imines

1,3-Dipolar cycloadditions of azomethine imines

Generation of crystal structures using known crystal structures as analogues

Asymmetric Synthesis of C1-Chiral THIQs with Imines in Isoquinoline Rings

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