Brønsted acid-catalyzed Mannich reaction through dual activation of aldehydes and N-Boc-imines

Kano, Taichi; Aota, Yusuke; Asakawa, Daisuke; Maruoka, Keiji

doi:10.1039/c5cc07290e

Cited by 25 publications

(9 citation statements)

References 21 publications

(1 reference statement)

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“…These approaches resemble the Ag-catalyzed reaction previously developed by Hoveyda and Snapper, , where propargylamines are synthesized through the addition of carbon nucleophiles to alkynyl imines. Maruoka and co-workers developed a stereoselective Mannich-type reaction of in situ generated C-alkynyl imines 380 with acetylacetone , and aliphatic aldehydes catalyzed by chiral Brønsted acids 376 (Scheme ). Interestingly, a racemic version of the reaction can be performed in the presence of Cu(OTf) 2 in place of the Brønsted acid catalyst.…”

Section: Synthesis Of Propargylaminesmentioning

confidence: 99%

Synthesis and Reactivity of Propargylamines in Organic Chemistry

et al. 2017

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Propargylamines are a versatile class of compounds which find broad application in many fields of chemistry. This review aims to describe the different strategies developed so far for the synthesis of propargylamines and their derivatives as well as to highlight their reactivity and use as building blocks in the synthesis of chemically relevant organic compounds. In the first part of the review, the different synthetic approaches to synthesize propargylamines, such as A couplings and C-H functionalization of alkynes, have been described and organized on the basis of the catalysts employed in the syntheses. Both racemic and enantioselective approaches have been reported. In the second part, an overview of the transformations of propargylamines into heterocyclic compounds such as pyrroles, pyridines, thiazoles, and oxazoles, as well as other relevant organic derivatives, is presented.

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Section: Synthesis Of Propargylaminesmentioning

confidence: 99%

Synthesis and Reactivity of Propargylamines in Organic Chemistry

et al. 2017

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“…The classic strategy for preparing chiral propargylamines involves the asymmetric nucleophilic alkynylation of imines, thereby creating the chiral propargylic stereocenter in a C(sp)−C(sp 3 ) bond‐forming event (Scheme A) . Recently, several elegant asymmetric syntheses of propargylamines have been developed by utilizing electrophilic alkynyl imines that react with alkyl zinc reagents, silyl enol ethers, silyl ketene acetals,, enolizable aldehydes,– acetylacetone, β‐keto esters, malonate (thio)esters, and glycine Schiff bases as suitable nucleophiles; in these approaches, a C(sp 3 )−C(sp 3 ) bond formation is involved (Scheme B). However, to the best of our knowledge, chiral propargylamines still have not been synthesized in an arylation approach, which would involve a distinctive and complementary C(sp 2 )−C(sp 3 ) bond formation (Scheme C).…”

Section: Methodsmentioning

confidence: 99%

An Arylation Strategy to Propargylamines: Catalytic Asymmetric Friedel–Crafts‐type Arylation Reactions of C‐Alkynyl Imines

Wang

Jiang

et al. 2016

Angewandte Chemie

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The first arylation strategy for the synthesis of enantioenriched propargylamines is disclosed. This approach, which is complementary to previous alkynylation and alkylation strategies,involves aC(sp 2 ) À C(sp 3 )bond formation, and is based on the first asymmetric Friedel-Crafts-type arylation reaction of C-alkynyl imines.A symmetric Friedel-Crafts reactions with electron-deficient phenols,alongstanding unsolved challenge,h ave thus been realized for the first time, enabled by the combination of our recently introduced Calkynyl N-Boc-protected N,O-acetals as electrophiles and chiral phosphoric acids as catalysts.T he synthetic utility of the resulting structurally diverse and polyfunctional chiral propargylamines was demonstrated by as eries of selective transformations,i ncluding controlled reduction of the alkynyl group and iterative cross-couplings.

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“…[34,35] Interestingly,w hen aldehydes are used in this reaction, a dual activation of the aldehyde and the alkynyl N-Boc imine was observed under Brønsted acid catalysis. [36,37] The authors proposed that tert-butyl carbamate, released in the generation of the N-Boc imine, reacts with the aldehyde to generate the correspondingnucleophilic enecarbamate (Scheme 8).…”

Section: Nn-diacylaminals As Imine Surrogatesmentioning

confidence: 99%

N,N‐Diacylaminals as Emerging Tools in Synthesis: From Peptidomimetics to Asymmetric Catalysis

López

Palomo

2020

Chemistry A European J

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N,N-Diacylaminals are flexible molecular scaffolds that have commonly been utilized as amide surrogates in peptidomimetics. The singularities of this motif as an N-acyl imine equivalenta nd as hydrogen-bond donor have recently openedn ew synthetic opportunities,e specially in the field of asymmetric catalysis. This concept article highlightst his diverse synthetic potentiala nd provides the elements necessary for furtherd evelopments.

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Brønsted acid-catalyzed Mannich reaction through dual activation of aldehydes and N-Boc-imines

Cited by 25 publications

References 21 publications

Synthesis and Reactivity of Propargylamines in Organic Chemistry

Synthesis and Reactivity of Propargylamines in Organic Chemistry

An Arylation Strategy to Propargylamines: Catalytic Asymmetric Friedel–Crafts‐type Arylation Reactions of C‐Alkynyl Imines

N,N‐Diacylaminals as Emerging Tools in Synthesis: From Peptidomimetics to Asymmetric Catalysis

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