Threonine-surfactant organocatalysts for the highly diastereo- and enantioselective direct anti-Mannich reactions of hydroxyacetone

Wu, Chuanlong; Fu, Xiangkai; Ma, Xuebing; Shi, Li; Li, Chao

doi:10.1016/j.tetlet.2010.08.085

Cited by 26 publications

(15 citation statements)

References 44 publications

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“…Through a series of disclosures, during the time period from 2010 to 2012, Xiangkai Fu and co-workers detailed the preparation of amphiphilic organocatalysts from serine, threonine and cysteine by acidic O -acylation, as well as their use in asymmetric organocatalysis [ 54 – 61 ]. Chemoselective O -acylation of serine, threonine and cysteine in CF 3 CO 2 H with a range of acyl chlorides, followed by crystallization of the product directly from the reaction mixture by addition of Et 2 O, furnished a comprehensive collection of amphiphilic, chiral organocatalysts ( Scheme 10 ).…”

Section: Reviewmentioning

confidence: 99%

Chemoselective O-acylation of hydroxyamino acids and amino alcohols under acidic reaction conditions: History, scope and applications

Kristensen¹

2015

Beilstein J. Org. Chem.

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SummaryAmino acids, whether natural, semisynthetic or synthetic, are among the most important and useful chiral building blocks available for organic chemical synthesis. In principle, they can function as inexpensive, chiral and densely functionalized starting materials. On the other hand, the use of amino acid starting materials routinely necessitates protective group chemistry, and in reality, large-scale preparations of even the simplest side-chain derivatives of many amino acids often become annoyingly strenuous due to the necessity of employing protecting groups, on one or more of the amino acid functionalities, during the synthetic sequence. However, in the case of hydroxyamino acids such as hydroxyproline, serine, threonine, tyrosine and 3,4-dihydroxyphenylalanine (DOPA), many O-acyl side-chain derivatives are directly accessible via a particularly expedient and scalable method not commonly applied until recently. Direct acylation of unprotected hydroxyamino acids with acyl halides or carboxylic anhydrides under appropriately acidic reaction conditions renders possible chemoselective O-acylation, furnishing the corresponding side-chain esters directly, on multigram-scale, in a single step, and without chromatographic purification. Assuming a certain degree of stability under acidic reaction conditions, the method is also applicable for a number of related compounds, such as various amino alcohols and the thiol-functional amino acid cysteine. While the basic methodology underlying this approach has been known for decades, it has evolved through recent developments connected to amino acid-derived chiral organocatalysts to become a more widely recognized procedure for large-scale preparation of many useful side-chain derivatives of hydroxyamino acids and related compounds. Such derivatives are useful in peptide chemistry and drug development, as amino acid amphiphiles for asymmetric catalysis, and as amino acid acrylic precursors for preparation of catalytically active macromolecular networks in the form of soluble polymers, crosslinked polymer beads or nanoparticulate systems. The objective of the present review is to increase awareness of the existence and convenience of this methodology, assess its competitiveness compared to newer and more elaborate procedures for chemoselective O-acylation reactions, spur its further development, and finally to chronicle the informative, but poorly documented history of its development.

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Section: Reviewmentioning

confidence: 99%

Chemoselective O-acylation of hydroxyamino acids and amino alcohols under acidic reaction conditions: History, scope and applications

Kristensen¹

2015

Beilstein J. Org. Chem.

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“…The catalytic effect of isosteviol-amino acid conjugates 1-3 for asymmetric direct Mannich were investigated using the reaction of p-nitrobenzaldehyde, aniline and hydroxyacetone as a model with 10 mol% catalysts loading in DMF, the configuration of Mannich products was determined by NMR data and chiral phase HPLC analysis comparison with that in the literature, 13,18 and the results were summarized in Table 1. First, the catalytic activity and stereoselectivity of L-proline derivative 1b was higher than that of 1a, which afforded the syn-isomer as main product in 91% yield with 84∶16 dr (syn∶anti) and 99% ee value within 5 h (Entry 2).…”

Section: Resultsmentioning

confidence: 99%

“…Besides, acylic amino acids and their derivatives were also investigated for the direct one-pot threecomponent Mannich reactions. [15][16][17][18] However, it should be noted that most of the organocatalysts were prepared with strenuous procedure, which needed tiresome purification of chromatography and created the added hurdles for industrial production. Chiral 1,2-amino alcohols are the common structural motifs found in a vast array of natural and biologically active molecules, 19 and can be constructed via Mannich reaction using hydroxyketone as donor molecule.…”

Section: Introductionmentioning

confidence: 99%

Isosteviol‐amino Acid Conjugates as Highly Efficient Organocatalysts for the Asymmetric One‐pot Three‐component Mannich Reactions

Qin

Wang

et al. 2011

Chin. J. Chem.

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Isosteviol-amino acid conjugates were synthesized and used as chiral catalysts for the asymmetric three-component Mannich reaction with hydroxyacetone as donor molecule. Good yields (up to 98%) and excellent stereoselectivities (up to 97∶3 dr and 99% ee) were achieved in a short reaction time. In addition, syn-or anti-configurations of α-hydroxy-β-amino carbonyl compounds were obtained as main products with different chiral catalysts.

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“…In 2011, Fu et al introduced l-threonine derivatives as novel organocatalysts for enantioselective direct anti-Mannich reactions of hydroxyacetone 370 with aldehydes 371a-f and anilines 372a-f. [164] When the reaction was promoted by l-threonine-derived catalyst 373 in 1-methyl-2-pyrrolidinone (NMP) as the solvent, it afforded the corresponding anti-1,2-amino alcohols 374a-l in good yields (75-93%) and high enantioselectivities of up to 99% ee, as shown in Scheme 95.…”

Section: Multicomponent Reactions Based On the Mannich Reactionmentioning

confidence: 99%

Recent Developments in Asymmetric Organocatalytic Domino Reactions

2012

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Since about the year 2000, the research area of asymmetric organocatalysis has grown rapidly to become one of the most fascinating and current fields in organic chemistry. In the last years, asymmetric domino reactions have widely benefited from this fast-growing field, as exemplified by the development of an explosive number of novel and powerful asymmetric organocatalytic domino processes, which allowed the easy construction of complex chiral molecular architectures from simple materials with high yields and very often remarkable enantioselectivities in a metal-free environment. Indeed, the possibility to join two or more organocatalytic reactions in one asymmetric domino process has become a challenging goal for chemists, due to several advantages from economical and environmental points of view, avoiding costly protecting groups and time-consuming purification procedures after each step, for example. This review aims to update the latest developments of this hot and fascinating field, covering the literature since the beginning of 2009.

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Threonine-surfactant organocatalysts for the highly diastereo- and enantioselective direct anti-Mannich reactions of hydroxyacetone

Cited by 26 publications

References 44 publications

Chemoselective O-acylation of hydroxyamino acids and amino alcohols under acidic reaction conditions: History, scope and applications

Chemoselective O-acylation of hydroxyamino acids and amino alcohols under acidic reaction conditions: History, scope and applications

Isosteviol‐amino Acid Conjugates as Highly Efficient Organocatalysts for the Asymmetric One‐pot Three‐component Mannich Reactions

Recent Developments in Asymmetric Organocatalytic Domino Reactions

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