Design of Axially Chiral Dicarboxylic Acid for Asymmetric Mannich Reaction of Arylaldehyde <i>N</i>-Boc Imines and Diazo Compounds

Hashimoto, Takuya; Maruoka, Keiji

doi:10.1021/ja0713375

Cited by 229 publications

(98 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…19 Although the chiral phosphoric acid catalyzed Mannich reaction of N acyl imines with diazoacetates had previously been reported by Terada, 20 the use of the dicarboxylic acid catalyst was found to be crucially important in the case of N Boc imines. The use of diazoacetamide instead of diazo ester was possible, leading to an asymmetric synthesis of trans aziridines in good yields with excellent diastereo and enantioselectivities (Scheme 12b).…”

Section: With Axially Chiral Dicarboxylic Acids Based Onmentioning

confidence: 99%

The Design of Environmentally-Benign, High-Performance Organocatalysts for Asymmetric Catalysis

Sakamoto¹,

Maruoka

2017

J. Synth. Org. Chem. Jpn.

Self Cite

View full text Add to dashboard Cite

By the end of the 20 th century several advantages of organocatalysis, for example environmental friendliness, operational simplicity, mild reaction conditions etc., had led to its recognition as a powerful principle for the establishment of practical organic synthetic methods. Over the two decades since then tremendous effort has been devoted to the design of novel organocatalysts able to realize unprecedented reactions. In this review our recent results on the design and development of various types of organocatalysts, such as organobase, organoacid, organoacid/base and organoradical catalysts, and their application to a wide variety of synthetic transformations are described. Scheme 1. Asymmetric, phase transfer alkylation of a prochiral, protected glycine derivative.

show abstract

Section: With Axially Chiral Dicarboxylic Acids Based Onmentioning

confidence: 99%

The Design of Environmentally-Benign, High-Performance Organocatalysts for Asymmetric Catalysis

Sakamoto¹,

Maruoka

2017

J. Synth. Org. Chem. Jpn.

Self Cite

View full text Add to dashboard Cite

show abstract

“…Bei einer Reihe von Arylaldimiden mit verschiedenen elektronischen Eigenschaften wurden gute Enantioselektivitäten beobachtet. [30] Schema 2. Diastereoselektive Brønsted-Säure-katalysierte Aza-DarzensReaktion.…”

Section: Brønsted-säure-katalysierte Addition An Azomethineunclassified

Protonierung oder Alkylierung? Stereoselektive Brønsted‐Säure‐katalysierte C‐C‐Verknüpfungen mit Diazoalkanen

2010

View full text Add to dashboard Cite

In den letzten Jahren wurden neue Aktivierungsmöglichkeiten für Diazoalkane entdeckt und bereits umfangreich angewendet. Mit chiralen und achiralen Brønsted‐Säuren als Katalysatoren gelangen Kohlenstoff‐Kohlenstoff‐ und Kohlenstoff‐Heteroatom‐Verknüpfungen mit einer zunehmenden Zahl von Diazoalkan‐Derivaten. Auf diesem Weg lassen sich sehr einfach in struktureller und stereochemischer Hinsicht komplizierte Verbindungen erhalten. Außerdem wird auch die konkurrierende Protonierung der Diazoverbindung umgangen – eine Reaktion, die seit langem zur effizienten Veresterung von Carbonsäuren genutzt wird. Achirale Brønsted‐Säuren als Katalysatoren erreichen hohe Diastereoselektivitäten, und chirale Brønsted‐Säuren führen zu den gewünschten Produkten mit sowohl hoher Diastereo‐ als auch Enantioselektivität. Seit einiger Zeit gibt es auch Systeme zur Kohlenstoff‐Kohlenstoff‐Verknüpfung, die eine Brønsted‐Säure mit einer Lewis‐Säure oder einer Übergangsmetallverbindung kombinieren.

show abstract

“…图式 1 重氮化合物的典型反应类型 Scheme 1 Typical reaction types of diazo compounds 在重氮化合物的转化过程中, 过渡金属催化的反应是一类重要的途径 [4] : 其中, 既包括了传统的经由过渡 [11,12] . …”

unclassified

Nitrogen Group Retaining Reaction in the Transformation of Diazo Compounds

Qiu¹,

Qiu²,

Ma³

et al. 2016

Acta Chim. Sinica

View full text Add to dashboard Cite

Diazo compounds represent a type of very important synthetic intermediates, which demonstrate wide applications in organic synthesis, continuous-in-flow technology, polymer synthesis, medicinal chemistry, chemical biology, material science and many other fields. On the other hand, diazo intermediates can be easily prepared from commercial available substrates through facile transformations, such as base-promoted decomposition of N-tosylhydrazones, diazo-transfer reaction, diazotization of alkyl amines, oxidation of hydrazones, decomposition of N-nitroso compounds. Traditional transformations of diazo compounds include nucleophilic addition/substitution by using diazo compounds as the nucleophiles, ylide type reactions, dimerization or olefination, Wolff rearrangement, transition-metal-carbene or carbenoid mediated X-H insertion reactions, catalytic cyclopropanations or cyclopropenations, and the recently developed transition-metal-catalyzed carbenoid cross-coupling reactions. In addition to these classic reactions, the diazo compounds also undergo nitrogen group retaining reactions, in which the diazo moiety is incorporated into the nitrogen-containing moiety in the target molecules. This strategy has provided an efficient and selective synthetic approach towards nitrogen atom containing functional molecules, especially for the synthesis of various N-heterocyclic compounds. Among them, the enantioselective C-N bond forming reaction as well as the asymmetric N-heterocyclic scaffold construction has important synthetic value and remains great challenge to the organic chemists. Thus, nitrogen component retaining reactions of diazo compounds has opened up a superior avenue in organic synthesis. Considering about the significant importance and the great growth in the past decade of this area, this review article will focus on the nitrogen group retaining reaction of diazo compounds. According to the reaction mechanism of these transformations, this review will be divided into the following parts: diazo compounds as nucleophiles, diazo compounds as 1,3-dipoles in cycloaddition reaction, diazo compounds as electrophiles, intramolecular reactions of vinyldiazo compounds, reduction reaction, and miscellaneous transformation. We hope that this review will corroborate the practical use of this research area as a convenient and valuable synthetic strategy. Keywords diazo compound; organic synthesis; N-heterocycle; cycloaddition

show abstract

Design of Axially Chiral Dicarboxylic Acid for Asymmetric Mannich Reaction of Arylaldehyde N-Boc Imines and Diazo Compounds

Abstract: An axially chiral dicarboxylic acid has been prepared as a new class of chiral hydrogen-bonding catalysts and applied to the highly enantioselective Mannich reaction of arylaldehyde N-Boc imines and diazo compounds.

Cited by 229 publications

References 17 publications

The Design of Environmentally-Benign, High-Performance Organocatalysts for Asymmetric Catalysis

The Design of Environmentally-Benign, High-Performance Organocatalysts for Asymmetric Catalysis

Protonierung oder Alkylierung? Stereoselektive Brønsted‐Säure‐katalysierte C‐C‐Verknüpfungen mit Diazoalkanen

Nitrogen Group Retaining Reaction in the Transformation of Diazo Compounds

Contact Info

Product

Resources

About