A new approach to the asymmetric Mannich reaction catalyzed by chiral N,N′-dioxide–metal complexes

Lian, Xiangjin; Lin, Lili; Fang, Kai; Ma, Buyong; Liu, Xiaohua

doi:10.1039/c6sc03902b

Cited by 74 publications

(34 citation statements)

References 48 publications

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“…The Mannich reaction is one of the most important basic reaction types in organic chemistry for C−C and C−N bond formation . The classical Mannich product arises from the condensation reaction of a compound containing at least one active hydrogen atom with formaldehyde and a secondary amine .…”

Section: Introductionmentioning

confidence: 99%

“…The Mannich reaction is one of the most important basic reaction types in organic chemistry for CÀ C and CÀ N bond formation. [1][2][3] The classical Mannich product arises from the condensation reaction of a compound containing at least one active hydrogen atom with formaldehyde and a secondary amine. [4] A special variation of this latter reaction when formaldehyde is replaced by benzaldehyde, the secondary amine by ammonia, and the CÀ H acid by an electron-rich aromatic compound such as 2-naphthol.…”

Section: Introductionmentioning

confidence: 99%

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Ortho‐Quinone Methide Driven Synthesis of New O,N‐ or N,N‐Heterocycles

et al. 2019

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To synthesize functionalized Mannich bases that can serve two different types of ortho ‐quinone methide ( o ‐QM) intermediates, 2‐naphthol and 6‐hydroxyquinoline were reacted with salicylic aldehyde in the presence of morpholine. The Mannich bases that can form o ‐QM and aza ‐ o ‐QM were also synthesized by mixing 2‐naphthol, 2‐nitrobenzaldehyde, and morpholine followed by reduction of the nitro group. The highly functionalized aminonaphthol derivatives were then tested in [4+2] cycloaddition with different cyclic imines. The reaction proved to be both regio‐ and diastereoselective. In all cases, only one reaction product was obtained. Detailed structural analyses of the new polyheterocycles as well as conformational studies including DFT modelling were performed. The relative stability of o ‐QMs/ aza‐o ‐QM were also calculated, and the regioselectivity of the reactions could be explained only when the cycloaddition started from aminodiol 4 . It was summarized that starting from diaminonaphthol 25 , the regioselectivity of the reaction is driven by the higher nucleophilicity of the amino group compared with the hydroxy group. 12H‐benzo[a]xanthen‐12‐one ( 11 ), formed via o ‐QM formation, was isolated as a side product. The proton NMR spectrum of 11 proved to be very unique from NMR point of view. The reason for the extreme low‐field position of proton H‐1 could be accounted for by theoretical calculation of structure and spatial magnetic properties of the compound in combination of ring current effects of the aromatic moieties and steric compression within the heavily hindered H(1)‐C(1)‐C(12b)‐C(12a)‐C(12)=O structural fragment.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Ortho‐Quinone Methide Driven Synthesis of New O,N‐ or N,N‐Heterocycles

et al. 2019

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“…at room temperature. The yield was significantly decreased when organic bases were used such as DIPEA, Et 3 N ( Table 1, entries [14][15]. Other bases did not lead to any improvement in the yield (Table 1, entry 8 vs entries 9-13).…”

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confidence: 99%

“…[12] During the past a few years, 1,3,5-triazinanes have attracted increasing attention in the synthesis of N-containing compounds. [13] Subsequently, Feng [14] and Kang [15] reported the asymmetric Mannich reaction of 1,3,5-triazinanes, respectively. [13] Subsequently, Feng [14] and Kang [15] reported the asymmetric Mannich reaction of 1,3,5-triazinanes, respectively.…”

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confidence: 99%

Inverse‐Electron‐Demand [4+2]‐Cycloaddition of 1,3,5‐triazinanes: Facile Approaches to Tetrahydroquinazolines

Zheng

Liang

et al. 2018

Adv Synth Catal

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An unprecedented inverse-electron-demand [4 + 2] cycloaddition reaction of in situ generated aza-o-quinone methides with 1,3,5-triazinanes has been developed under mild conditions, providing an efficient and mild approach to synthesize tetrahydroquinazolines in high yields (up to 99%) with excellent functional group tolerance. This protocol represents the first example of inverse-electron-demand [4 + 2] cycloaddition reaction of 1,3,5-triazinanes.

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“…[5j] Our group demonstrated conversion with chalcogenyl halides to accomplish the first 1,3-halochalcogenationo fD -A cyclopropanes (Scheme 1c). 1,3,5-Triaryl-1,3,5triazinanes show nucleophilic reactivity at the nitrogen, but have also been employed as stable precursors of formaldimines and have been implemented as effective aminomethylation reagents by Krische et al [8] and as Mannich-type reagents by Feng et al [9] Moreover,aseries of gold-catalyzed cycloaddition reactions have been established to afford nitrogen-containing heterocycles. Such as equence would afford compounds with two amino groups located at the 1,4-positions,i no ther words b,g'diamino diester derivatives,w hich are important compounds for pharmaceutical research (Scheme 1d).…”

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confidence: 99%

Ring‐Opening 1‐Amino‐3‐aminomethylation of Donor–Acceptor Cyclopropanes via 1,3‐Diazepanes

2017

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The first ring-opening reaction of donor-acceptor cyclopropanes to give diamines is reported. For this reaction, a 1,3-bisfunctionalization was developed using cyclopropanes, triazinanes, and Sc(OTf) as the catalyst, followed by treatment with acid. The reaction proceeds under very mild conditions and tolerates many functional groups. Moreover, a library of various 1,3-diazepanes, which arise as intermediates of the first formal aza-[4+3]-cycloaddition reaction with donor-acceptor cyclopropanes, was synthesized.

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A new approach to the asymmetric Mannich reaction catalyzed by chiral N,N′-dioxide–metal complexes

Abstract: An efficient asymmetric Mannich-type reaction between α-tetralone-derived β-keto esters/amides and 1,3,5-triaryl-1,3,5-triazinanes was realized catalyzed by chiral N,N'–dioxide-Ni(ii)/Mg(ii) complexes.

Cited by 74 publications

References 48 publications

Ortho‐Quinone Methide Driven Synthesis of New O,N‐ or N,N‐Heterocycles

Ortho‐Quinone Methide Driven Synthesis of New O,N‐ or N,N‐Heterocycles

Inverse‐Electron‐Demand [4+2]‐Cycloaddition of 1,3,5‐triazinanes: Facile Approaches to Tetrahydroquinazolines

Ring‐Opening 1‐Amino‐3‐aminomethylation of Donor–Acceptor Cyclopropanes via 1,3‐Diazepanes

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