Ueber die Acylirung der Alkohole und Phenole in Pyridinlösung

Einhorn, Alfred; Hollandt, Friedrich; Einhorn, M.

doi:10.1002/jlac.18983010111

Cited by 131 publications

(17 citation statements)

References 14 publications

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“…One classic method for the acylation of alcohols employs pyridine, which was originally believed to act as a general base catalyst, and an acid chloride or anhydride. [51] Although these conditions are mild, the reaction rates are slow, especially with hindered secondary and tertiary alcohols.…”

Section: Lewis Base Catalyzed Acylationsmentioning

confidence: 99%

Lewis Base Catalysis in Organic Synthesis

2008

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The legacy of Gilbert Newton Lewis (1875-1946) pervades the lexicon of chemical bonding and reactivity. The power of his concept of donor-acceptor bonding is evident in the eponymous foundations of electron-pair acceptors (Lewis acids) and donors (Lewis bases). Lewis recognized that acids are not restricted to those substances that contain hydrogen (Brønsted acids), and helped overthrow the "modern cult of the proton". His discovery ushered in the use of Lewis acids as reagents and catalysts for organic reactions. However, in recent years, the recognition that Lewis bases can also serve in this capacity has grown enormously. Most importantly, it has become increasingly apparent that the behavior of Lewis bases as agents for promoting chemical reactions is not merely as an electronic complement of the cognate Lewis acids: in fact Lewis bases are capable of enhancing both the electrophilic and nucleophilic character of molecules to which they are bound. This diversity of behavior leads to a remarkable versatility for the catalysis of reactions by Lewis bases.

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Section: Lewis Base Catalyzed Acylationsmentioning

confidence: 99%

Lewis Base Catalysis in Organic Synthesis

2008

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“…1, 2 An important facet of this broad domain is the asymmetric nonenzymatic 3 catalysis of acyl-transfer by chiral organic nucleophiles such as tertiary amines, 4-7 phosphines, 8 N-heterocyclic carbenes 9,10 and secondary alcohols. 11 Although it has been over a century since the discovery of pyridine-promoted alcohol acylation, 12 the design of efficient and selective chiral pyridine-based catalysts for these reactions is a young field less than 10 years old. The desymmetrisation of the 'hypernucleophilic' achiral catalyst 4-N,N-dimethylaminopyridine (DMAP) 13, 14 via one of three general strategies, (the introduction of 'planar chirality' either 2,3-pyridofused 15 or installed at the C-3-position of the pyridine ring, 16 the use of axially chiral substituents at C-3 17 or the installation of tetrahedral chirality at either C-4, 18-23 or C-3, 24-27 ) has proven a particularly productive approach which has given rise to a number of highly selective chiral catalysts for the kinetic resolution (KR) of sec-alcohols and other asymmetric acyl-transfer processes.…”

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confidence: 99%

Asymmetric acyl-transfer promoted by readily assembled chiral 4-N,N-dialkylaminopyridine derivatives

et al. 2006

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The development of a new class of chiral 4-N,N-dialkylaminopyridine acyl-transfer catalysts capable of exploiting both van der Waals (p) and H-bonding interactions to allow remote chiral information to stereochemically control the kinetic resolution of sec-alcohols with moderate to excellent selectivity (s = 6-30). Catalysts derived from (S)-a,a-diarylprolinol are considerably superior to analogues devoid of a tertiary hydroxyl moiety and possess high activity and selectivity across a broad range of substrates.Asymmetric organocatalysis has recently been propelled from relative obscurity to the forefront of contemporary organic chemistry research and is fast-becoming a key strategy in enantioselective synthesis. 1, 2 An important facet of this broad domain is the asymmetric nonenzymatic 3 catalysis of acyl-transfer by chiral organic nucleophiles such as tertiary amines, 4-7 phosphines, 8 N-heterocyclic carbenes 9,10 and secondary alcohols. 11 Although it has been over a century since the discovery of pyridine-promoted alcohol acylation, 12 the design of efficient and selective chiral pyridine-based catalysts for these reactions is a young field less than 10 years old. The desymmetrisation of the 'hypernucleophilic' achiral catalyst 4-N,N-dimethylaminopyridine (DMAP) 13,14 via one of three general strategies, (the introduction of 'planar chirality' either 2,3-pyridofused 15 or installed at the C-3-position of the pyridine ring, 16 the use of axially chiral substituents at C-3 17 or the installation of tetrahedral chirality at either C-4, 18-23 or C-3, 24-27 ) has proven a particularly productive approach which has given rise to a number of highly selective chiral catalysts for the kinetic resolution (KR) of sec-alcohols and other asymmetric acyl-transfer processes. 15,27, 28 The design of such systems is complicated by an activityselectivity conundrum: i.e. to maximise the effectiveness of catalyst stereochemical information it is desirable to install chiral groups as close to the nucleophilic ring nitrogen as possible, however, bulky substituents in the vicinity of the same strongly attenuate catalyst activity. 14,17c,29 A successful (i.e. active and selective) catalyst design must necessarily embody a compromise between these opposing constraints.One appealing solution to this problem (inspired by enzymatic systems) is the design of promoters capable of operating by an 'induced-fit' mechanism, in which the catalyst undergoes a a Centre for Synthesis and Chemical Biology, School of Chemistry, University of Dublin, Trinity College, Dublin 2, Ireland. E-mail: connons@tcd.ie; Fax: +353 1 6712826; Tel: +353 1 6081306 b School of Chemistry, University of Dublin, Trinity College, Dublin 2, Ireland † Electronic supplementary information (ESI) available: General experimental procedures and details, characterisation data for the synthesis of catalysts 14 and 15, 1 H and 13 C NMR spectra for 6 and 7 (and their precursors), X-ray crystal structure data for 6-Bn, atomic coordinates from the DFT calculations and CSP...

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“…The results obtained for the receptor affinities together with those of the hydrolytic stabilities are surprising: Though some derivatives like the halogenated esters (5)(6)(7)(8) are rapidly hydrolyzed to 1, they have even higher RBA-values than 1. Therefore, receptor binding may occur rapidly before hydrolysis.…”

Section: Biologicd Properties and Discussionmentioning

confidence: 96%

Influence of Derivatisation of the Hydroxy Groups in 1,1‐Bis‐(4‐hydroxyphenyl)‐2‐phenylbut‐1‐ene on Estradiol Receptor Affinity and Mammary Tumor Inhibiting Properties

Schuderer

Schneider

1987

Archiv der Pharmazie

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The phenolic hydroxy groups of l,l-bis-(4-hydroxyphenyl)-2-phenylbut-1-ene (1) were converted to esters of different chain length and degree of haiogen substitution, and to carbamate, imidoester and ether derivatives. Most of the products maintain the afinity to the estrogen receptor. The acetate 2 has a better antitumor potency than 1. EinfluB der Derivatisierung der Hydroxygruppen von l,i-Bis-(4-hydroxyphenyl)-2-phenyl-but-1-en auf die Estrogenrezeptoraffinitat und die wachstumshemmende Wirkung am MammacarzinomDie phenolischen OH-Gruppen des l,l-Bis-(4-hydroxyphenyl)-2-phenyl-but-l-ens (1) wurden zu Estern unterschiediicher Kettenlänge und Halogensubstitutionsgrads, zu Carbamaten, Imidoestern und Ethern derivatisiert. Die Afinität zum Estrogenrezeptor blieb bei den meisten Derivaten erhaiten. Das Acetat 2 hat eine bessere Antitumorwirkung als die Ausgangsverbindung 1. 0365-6233/87/0707-O635 S 02.50/0 O VCH Verlagsgesellschaft mbH, D-6940 Weinheim, 1987 Schuderer and SchneiderArch. Pharm. Schuderer and SchneiderArch. Pharm.

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Ueber die Acylirung der Alkohole und Phenole in Pyridinlösung

Cited by 131 publications

References 14 publications

Lewis Base Catalysis in Organic Synthesis

Lewis Base Catalysis in Organic Synthesis

Asymmetric acyl-transfer promoted by readily assembled chiral 4-N,N-dialkylaminopyridine derivatives

Influence of Derivatisation of the Hydroxy Groups in 1,1‐Bis‐(4‐hydroxyphenyl)‐2‐phenylbut‐1‐ene on Estradiol Receptor Affinity and Mammary Tumor Inhibiting Properties

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