Rational Design of an<scp>l</scp>-Histidine-Derived Minimal Artificial Acylase for the Kinetic Resolution of Racemic Alcohols

Ishihara, Kazuaki; Kosugi, Yuji; Akakura, Matsujiro

doi:10.1021/ja045850j

Cited by 101 publications

(35 citation statements)

References 12 publications

(6 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[2] In both areas the use of sterically hindered anhydrides enjoys widespread application, usually for the sake of reduced reactivity (of the acylation product) or enhanced selectivity (of the acylation process). This type of acylation reaction can be catalyzed efficiently with basic catalysts based on the pyridine [3][4][5] or imidazole [6][7][8] motif, but tertiary alkyl amines [9] or phosphines [10] have also been used successfully. In many cases the catalysts are derivatives of 4-(N,N-dimethylamino)pyridine (1, DMAP), whose catalytic potential is exploited widely in acyl-and other group-transfer reactions.…”

Section: Introductionmentioning

confidence: 99%

Steric Effects in the Uncatalyzed and DMAP‐Catalyzed Acylation of Alcohols—Quantifying the Window of Opportunity in Kinetic Resolution Experiments

Fischer

Zipse

2006

Chemistry A European J

View full text Add to dashboard Cite

The kinetics of the reaction of several alcohols (benzyl alcohol, ethanol, 1-phenylethanol, cyclohexanol, and 1-methyl-1-phenylethanol) with a selection of anhydrides (acetic anyhydride, propionic anhydride, isobutyric anhydride, isovaleric anhydride, and pivalic anhydride) as catalyzed by 4-(N,N-dimethylamino)pyridine (DMAP)/triethyl amine have been studied in CH(2)Cl(2) at 20 degrees C. In all cases the reaction kinetics can be described by rate laws containing a DMAP-catalyzed term and an uncatalyzed (background) term. The rate constants for the background reaction respond sensitively to changes in the steric demand of the alcohol and the anhydride substrates, making the reaction of cyclohexanol with acetic anhydride 526 times faster than the reaction with pivalic anhydride. Steric effects are even larger for the catalyzed reaction and the reactivity difference between acetic and pivalic anhydride exceeds a factor of 8000 for the reaction of cyclohexanol. There is, however, no linear correlation between the steric effects on the catalyzed and the uncatalyzed part. As a consequence there are substrate combinations with dominating catalytic terms (such as the reaction of benzyl alcohol with isobutyric anhydride), while other substrate combinations (such as the reaction of cyclohexanol with pivalic anhydride) are characterized through a dominating background process. The implications of these findings for the kinetic resolution of alcohols are discussed.

show abstract

Section: Introductionmentioning

confidence: 99%

Steric Effects in the Uncatalyzed and DMAP‐Catalyzed Acylation of Alcohols—Quantifying the Window of Opportunity in Kinetic Resolution Experiments

Fischer

Zipse

2006

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…[99] Zusätzlich konnte 153 effizient in der kinetischen Racematspaltung von Carbonsäuren eingesetzt werden (dies ist nicht der Hauptaspekt dieses Aufsatzes). [100] Ein ähnlicher, auf p-Methylhistidin basierender Ansatz wurde von Qu et al 2008 mit der Einführung des Katalysators 154 gewählt; mit 154 konnten gute Selektivitäten in der kinetischen Racematspaltung von (AE )-155 erzielt werden (SWerte bis zu 91; Schema 27).…”

unclassified

Organokatalytischer, enantioselektiver Acyltransfer auf racemische sowie meso‐Alkohole, ‐Amine und ‐Thiole

2011

View full text Add to dashboard Cite

Der Acyltransfer ist ein Paradebeispiel für den Transfer funktioneller Gruppen, sowohl in der Natur als auch im chemischen Labor. Acylierungen sind am Aufbau komplexer natürlicher Moleküle beteiligt und spielen eine entscheidende Rolle für den biologischen Energietransport. Die Charakterisierung kovalenter Acyl‐Enzym‐Intermediate trieb sowohl mechanistische Studien als auch die Entwicklung biomimetischer Verfahren an. Folglich verwendeten Chemiker zunächst die Werkzeuge der Natur in Form von Enzymen und natürlichen Alkaloiden als Katalysatoren, um schließlich eine Vielzahl kleiner, synthetischer Moleküle für den selektiven Acyltransfer zu entwickeln. Anders als die Natur nutzen Chemiker praktische Acylierungsreaktionen für die Stereoselektion und zum Schutz funktioneller Gruppen. Die Zahl der Studien zum Acyltransfer hat in den letzten 15 Jahren deutlich zugenommen. Dieser Aufsatz beschreibt diese Entwicklungen mit einem Schwerpunkt auf den im Titel genannten Substanzklassen.

show abstract

“…2 To the best of our knowledge, nonenzymatic method has been little known to date. 3 Recently, we have reported an efficient method for kinetic resolution of 1,2-diols 1. The method is based on recognition of 1 by copper ion associated with chiral ligand (R,R)-Ph-BOX 4 to afford the activated intermediates 2 followed by benzoylation (Scheme 1).…”

mentioning

confidence: 99%

Nonenzymatic Kinetic Resolution of 3-Hydroxyalkanamides with Chiral Copper Catalyst

Demizu¹,

Kubo²,

Matsumura³

et al. 2008

Synlett

View full text Add to dashboard Cite

We began our investigation by trying benzoylation of ethyl DL-3-hydroxybutanoate (4) as a model compound to see whether it could be recognized by chiral copper(II) complex or not. We found out the following, in the absence of copper(II) triflate and (R,R)-Ph-BOX the reaction of 4 with BzCl did not almost proceed, while in the presence of the catalysts, benzoylated product 5 was obtained in 19% yield based on 4. In contrast, DL-3-hydroxy-N-phenylbutanamide (6a) was benzoylated more efficiently in the presence of Cu(II)−(R,R)-Ph-BOX to afford benzoylated product 7a in 41% yield (Scheme 2). These results imply that 6a was efficiently recognized by Cu(II)−(R,R)-Ph-BOX complex.Abstract: Kinetic resolution of 3-hydroxyalkanamides with good to high selectivities was achieved by benzoylation using copper(II) triflate and (R,R)-Ph-BOX as a catalyst, which also mediated enantioselective tosylation of 2,2-bis(hydroxymethy)alkanamides with high efficiency.

show abstract

Rational Design of anl-Histidine-Derived Minimal Artificial Acylase for the Kinetic Resolution of Racemic Alcohols

Cited by 101 publications

References 12 publications

Steric Effects in the Uncatalyzed and DMAP‐Catalyzed Acylation of Alcohols—Quantifying the Window of Opportunity in Kinetic Resolution Experiments

Steric Effects in the Uncatalyzed and DMAP‐Catalyzed Acylation of Alcohols—Quantifying the Window of Opportunity in Kinetic Resolution Experiments

Organokatalytischer, enantioselektiver Acyltransfer auf racemische sowie meso‐Alkohole, ‐Amine und ‐Thiole

Nonenzymatic Kinetic Resolution of 3-Hydroxyalkanamides with Chiral Copper Catalyst

Contact Info

Product

Resources

About