Asymmetric [5+3] Formal Cycloadditions with Cyclic Enones through Cascade Dienamine–Dienamine Catalysis

Yin, Xiang; Zheng, Yi; Feng, Xinliang; Jiang, Kun; Wei, Xue-Zhen; Gao, Ning; Chen, Ying‐Chun

doi:10.1002/anie.201403753

Cited by 92 publications

(34 citation statements)

References 59 publications

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“…In our proposed mechanism for the cascade reaction (Scheme 3), the initial DVMA is followed by av inylogous Michael addition from the gposition of the cyclopentenone to the b-position of the butyrolactam. Migration of the CÀCdouble bond to the other side of the carbonyl group may be ascribed to an isomerization via the dienamine of cyclopentenone, [12] presumably driven by the thermodynamic stability of the product 6.…”

Section: Methodsmentioning

confidence: 99%

Direct Catalytic Asymmetric Doubly Vinylogous Michael Addition of α,β‐Unsaturated γ‐Butyrolactams to Dienones

Guo

Dai

et al. 2015

Angewandte Chemie

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An asymmetric doubly vinylogous Michael addition (DVMA) of a,b-unsaturated g-butyrolactams to sterically congested b-substituted cyclic dienones with high site-, diastereo-, and enantioselectivity has been achieved. An unprecedented DVMA/vinylogous Michael addition/isomerization cascade reaction affords chiral fused tricyclic g-lactams with four newly formed stereocenters.Remote stereocontrol in catalytic asymmetric reactions is am ajor challenge in modern organic synthesis. [1,2] Recently,a symmetric organocatalysis has been successfully applied to the functionalization of unsaturated carbonyl compounds at their g-, d-, and e-positions with high stereo-and site-selectivity.[1] Thet wo basic activation strategies exploit LUMO-lowering and HOMO-raising effects,whereby iminium ions and either di-or trienamines are formed by condensation of the carbonyl substrates with the amine function of chiral organocatalysts. [1,3] Melchiorre and coworkers achieved the d-functionalization of enones by using ac inchona-based primary amine,w hich forms an iminium ion with the polyunsaturated carbonyl substrate,t hus delivering the LUMO-lowering effect through the conjugated p system.[4] Enamine catalysis [5] was also successfully applied to vinylogous systems.D i-and trienamine catalysis, [5b,c] usually employing chiral secondary amines to activate the g and e sites of unsaturated aldehydes,has led for instance to aseries of Diels-Alder cycloadditions [5e] and other remote functionalization reactions. [6] In most studies as ingle vinylogous substrate,e ither the electrophilic or nucleophilic partner,w as used. [1,[3][4][5][6][7] In 2013 Jørgensen and co-workers reported the first organocatalytic doubly vinylogous Michael-type reaction, namely the 1,6-addition of alkylidene lactones to 2,4-dienals with the formation of an ew stereocenter (Scheme 1a).[8] It is significantly difficult to simultaneously activate the two vinylogous partners at their remote reactive sites whilst achieving high regio-, diastereo-, and enantiocontrol. Indeed, to the best of our knowledge there are no precedents for the catalytic, asymmetric doubly vinylogous Michael addition (DVMA) to 2,4-dienones,the much less reactive analogues of 2,4-dienals. Ther ealization of such ar eaction would prove the broad applicability of the organocatalytic vinylogous activation patterns,t hus representing as ignificant advance in the field. Moreover,asymmetric doubly vinylogous reactions naturally leave two unsaturated CÀCbonds in the product and provide

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Section: Methodsmentioning

confidence: 99%

Direct Catalytic Asymmetric Doubly Vinylogous Michael Addition of α,β‐Unsaturated γ‐Butyrolactams to Dienones

Guo

Dai

et al. 2015

Angewandte Chemie

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“…[7] Such cyclic 1-azadienes [8] could serve as good biselectrophilic partners in domino Michael addition-Mannich reactions. [7] Such cyclic 1-azadienes [8] could serve as good biselectrophilic partners in domino Michael addition-Mannich reactions.…”

Section: Introductionmentioning

confidence: 99%

“…At first, an array of aliphatic ketones were examined in reactions with 1-azadiene 3 a. On the other hand, some unsymmetrical ketones, including those possessing functional OTBS (tert-butyldimethylsilyl) and thioether groups, could be successfully utilized (entries [3][4][5][6][7][8][9]. On the other hand, some unsymmetrical ketones, including those possessing functional OTBS (tert-butyldimethylsilyl) and thioether groups, could be successfully utilized (entries [3][4][5][6][7][8][9].…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Formal [3+3] Cycloadditions of Ketones and Cyclic 1‐Azadienes by Cascade Enamine–Enamine Catalysis

Xiao

et al. 2015

Chemistry A European J

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An asymmetric formal [3+3] cycloaddition process with diversely structured aliphatic ketones and electron-deficient cyclic 1-azadienes was developed by cascade enamine-enamine catalysis of a cinchona-based primary amine. This sequence involved a domino Michael addition-Mannich reaction to afford spirocyclic architectures in excellent diastereo- and enantioselectivity. Importantly, high regioselectivity was realized for a number of unsymmetrical aliphatic ketone substrates.

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“…[7] Later,using different primary amine catalysts,Y ea nd co-workers demonstrated regioselective functionalization of 2-cyclopentenones from the vinylogous g' position (Scheme 1, path c). [7] Later,using different primary amine catalysts,Y ea nd co-workers demonstrated regioselective functionalization of 2-cyclopentenones from the vinylogous g' position (Scheme 1, path c).…”

mentioning

confidence: 99%

Vinylogous Reactivity of Cyclic 2‐Enones: Organocatalysed Asymmetric Addition to 2‐Enals to Synthesize Fused Carbocycles

et al. 2019

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Asymmetric [5+3] Formal Cycloadditions with Cyclic Enones through Cascade Dienamine–Dienamine Catalysis

Cited by 92 publications

References 59 publications

Direct Catalytic Asymmetric Doubly Vinylogous Michael Addition of α,β‐Unsaturated γ‐Butyrolactams to Dienones

Direct Catalytic Asymmetric Doubly Vinylogous Michael Addition of α,β‐Unsaturated γ‐Butyrolactams to Dienones

Enantioselective Formal [3+3] Cycloadditions of Ketones and Cyclic 1‐Azadienes by Cascade Enamine–Enamine Catalysis

Vinylogous Reactivity of Cyclic 2‐Enones: Organocatalysed Asymmetric Addition to 2‐Enals to Synthesize Fused Carbocycles

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