A N,N′-dioxide/Mg(OTf)<sub>2</sub> complex catalyzed enantioselective α-addition of isocyanides to alkylidene malonates

Luo, Weiwei; Yuan, Xiao; Lin, Lili; Zhou, Pengfei; Liu, Xiaohua; Feng, Xiaoming

doi:10.1039/c6sc00689b

Cited by 23 publications

(7 citation statements)

References 64 publications

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“…In contrast, when the reaction was performed without L-RaPr 2 , much less amount of the desired product was detected along with an undefined byproduct. Based on our previous works, a possible catalytic model was proposed. As depicted in Scheme , in the initial step, the two oxygens of amides and the two oxygens of the N , N′ -dioxide ligand L-RaPr 2 and dimethyl 2-benzylidenemalonate ( 3a ) coordinated with Mg II to give the intermediate T 1 .…”

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confidence: 99%

Enantioselective Synthesis of Hydrothiazole Derivatives via an Isocyanide-Based Multicomponent Reaction

Xiong

Dong

et al. 2019

Org. Lett.

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Catalytic asymmetric synthesis of hydrothiazole derivatives was developed via a well-organized formal [2 + 1 + 2] cycloaddition reaction triggered by asymmetric addition of isocyanide to alkylidene malonate. Various chiral hydrothiazole derivatives were readily provided in good yield with high enantioselectivity (up to 98% yield, 98.5:1.5 er) utilizing a chiral Mg(OTf)2/N,N′-dioxide complex as the catalyst under mild conditions. Based on the experimental studies and the structure of the catalyst, a possible catalytic cycle was proposed to elucidate the reaction process and activation mode.

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confidence: 99%

Enantioselective Synthesis of Hydrothiazole Derivatives via an Isocyanide-Based Multicomponent Reaction

Xiong

Dong

et al. 2019

Org. Lett.

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“…Based on the control experiments and the previous works 27,40,41 , a possible catalytic cycle along with a transition-state model were proposed to elucidate the reaction processes and the chiral induction. As depicted in Fig.…”

Section: Resultsmentioning

confidence: 99%

Asymmetric synthesis of tetrazole and dihydroisoquinoline derivatives by isocyanide-based multicomponent reactions

et al. 2019

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Although isocyanide-based multicomponent reactions were proven to be simple, elegant and facile strategies for the synthesis of highly valuable nitrogen-containing heterocycles, their asymmetric versions accessing to optically active nitrogen heterocyclic compounds are rather limited. Here, we illustrate that, relying on the enantioselective addition of simple isocyanides to C=C bonds, several isocyanide-based multicomponent reactions are realized in the presence of a chiral Mg II - N , N ʹ-dioxide catalyst. In the reaction among isocyanide, TMSN 3 , and alkylidene malonate, three- or four-component reactions could be precisely controlled by modulating reaction conditions, supplying two types of enantioenriched tetrazole-derivatives in moderate to high yields. Possible catalytic cycles via a key zwitterionic intermediate, and the vital roles of H 2 O or excess ligand are provided based on control experiments. Moreover, taking advantage of this zwitterionic intermediate as a 1,3-dipole, an enantioselective dearomative [3+2] annulation reaction of nonactivated isoquinolines is achieved, furnishing chiral 1,2-dihydroisoquinolines in good to excellent results.

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“…In the same year, Feng et al employed a catalyst system composed of Mg(OTf) 2 and chiral N,N′-dioxide ligand 105 in the synthesis of chiral 2-alkyl-5-aminooxazoles 108. 34 The process involved the Michael addition of -isocyanoacetamides 107 to alkylidene malonates 106 followed by an intramolecular cyclization reaction to provide chiral 2-alkyl-5-aminooxazoles 108 in variable yields (28-99%) and good enantioselectivities (72-96% ee) (Scheme 27).…”

Section: Formation Of One Ring Containing Several Heterocyclic Atomsmentioning

confidence: 99%

The Use of Domino Reactions for the Synthesis of Chiral Rings

Pellissier

2020

Synthesis

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This short review highlights the recent developments reported in the last four years on the asymmetric construction of chiral rings based on enantioselective domino reactions promoted by chiral metal catalysts.1 Introduction2 Formation of One Ring Containing One Nitrogen Atom3 Formation of One Ring Containing One Oxygen/Sulfur Atom4 Formation of One Ring Containing Several Heterocyclic Atoms5 Formation of One Carbon Ring6 Formation of Two Rings7 Conclusion

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A N,N′-dioxide/Mg(OTf)₂ complex catalyzed enantioselective α-addition of isocyanides to alkylidene malonates

Abstract: A simple and efficient catalytic asymmetric α-addition of isocyanides to alkylidene malonates was realized using a chiral N,N′-dioxide/MgII catalyst. A variety of 2-alkyl-5-aminoxazoles were obtained in up to 99% yield and 96% ee, and could be converted to imides and dipeptides.

Cited by 23 publications

References 64 publications

Enantioselective Synthesis of Hydrothiazole Derivatives via an Isocyanide-Based Multicomponent Reaction

Enantioselective Synthesis of Hydrothiazole Derivatives via an Isocyanide-Based Multicomponent Reaction

Asymmetric synthesis of tetrazole and dihydroisoquinoline derivatives by isocyanide-based multicomponent reactions

The Use of Domino Reactions for the Synthesis of Chiral Rings

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A N,N′-dioxide/Mg(OTf)2 complex catalyzed enantioselective α-addition of isocyanides to alkylidene malonates

Abstract: A simple and efficient catalytic asymmetric α-addition of isocyanides to alkylidene malonates was realized using a chiral N,N′-dioxide/MgII catalyst. A variety of 2-alkyl-5-aminoxazoles were obtained in up to 99% yield and 96% ee, and could be converted to imides and dipeptides.

Cited by 23 publications

References 64 publications

Enantioselective Synthesis of Hydrothiazole Derivatives via an Isocyanide-Based Multicomponent Reaction

Enantioselective Synthesis of Hydrothiazole Derivatives via an Isocyanide-Based Multicomponent Reaction

Asymmetric synthesis of tetrazole and dihydroisoquinoline derivatives by isocyanide-based multicomponent reactions

The Use of Domino Reactions for the Synthesis of Chiral Rings

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A N,N′-dioxide/Mg(OTf)₂ complex catalyzed enantioselective α-addition of isocyanides to alkylidene malonates