Highly stereoselective synthesis of aminoglycosides via rhodium-catalyzed and substrate-controlled aziridination of glycals

Lorpitthaya, Rujee; Sophy, K. B.; Kuo, Jer‐Lai; Liu, Xuewei

doi:10.1039/b823099b

Cited by 48 publications

(21 citation statements)

References 23 publications

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“…These computational results are in well agreement with the experiments. [30] The reaction time for glycal series 3 was slower than that for series 4 and 6, respectively.…”

Section: Full Papermentioning

confidence: 94%

Mechanistic Insights into the Substrate‐Controlled Stereochemistry of Glycals in One‐Pot Rhodium‐Catalyzed Aziridination and Aziridine Ring Opening

Lorpitthaya

Xie

Sophy

et al. 2009

Chemistry A European J

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We carried out a principle study on the reaction mechanism of rhodium-catalyzed intramolecular aziridination and aziridine ring opening at a sugar template. A sulfamate ester group was introduced at different positions of glycal to act as a nitrene source and, moreover, to allow the study of the relative reactivity of the nitrene transfer from different sites of the glycal molecule. The structural optimization of each intermediate along the reaction pathway was extensively done by using BPW91 functional. The crucial step in the reaction is the Rh-catalyzed nitrene transfer to the double bond of the glycal. We found that the reaction could proceed in a stepwise manner, whereby the N atom initially induced a single-bond formation with C1 on the triplet surface or in a single step through intersystem crossing (ISC) of the triplet excited state of the rhodium-nitrene transition state to the singlet ground state of the aziridine complexes. The relative reactivity for the conversion of the nitrene species to the aziridine obtained from the computed potential energy surface (PES) agrees well with the reaction time gained from experimental observation. The aziridine ring opening is a spontaneous process because the energy barrier for the formation of the transition state is very small and disappears in the solution calculations. The regio- and stereoselectivity of the reaction product is controlled by the electronic property of the anomeric carbon as well as the facial preference for the nitrene insertion, and the nucleophilic addition.

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“…These computational results are in well agreement with the experiments. [30] The reaction time for glycal series 3 was slower than that for series 4 and 6, respectively.…”

Section: Full Papermentioning

confidence: 94%

Mechanistic Insights into the Substrate‐Controlled Stereochemistry of Glycals in One‐Pot Rhodium‐Catalyzed Aziridination and Aziridine Ring Opening

Lorpitthaya

Xie

Sophy

et al. 2009

Chemistry A European J

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“…[39] Liu and co-workers have recently discovered that this rhodium(II) methodology can be made highly diastereoselective for the formation of a-and b-anomers of trans 1,2-aminoglycosides 47 and 48 by strategically tethering the sulfonamide at the C(6) or C(4) position of the glycal (Scheme 19). [40,41] It was reported that a wide range of oxygen nucleophiles, including carboxylic acids, can be added to the aziridine intermediates to react with high stereoselectivity. It is also noteworthy that the sulfonyloxy tether was readily replaced with a range of oxygen, sulfur and nitrogen nucleophiles following activation of the sulfonamate nitrogen with a carbamate group.…”

Section: Rhodium-catalysed Reactionsmentioning

confidence: 99%

Recent Developments in Methodology for the Direct Oxyamination of Olefins

Donohoe

Callens

Flores

et al. 2010

Chemistry A European J

267

116

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1,2-Amino alcohols are high-value, versatile functional groups that are found in scores of biologically active molecules and other interesting synthetic targets such as ligands and auxiliaries. Given their prominent position within organic compounds of import, it is no surprise to note that many routes have been developed to access this motif and there are many different starting points from which a synthetic chemist might embark on a synthesis. However, one particular approach stands out from the others, and this is the direct conversion of an alkene to a vicinal amino alcohol derivative (oxyamination). Research in this field has been particularly active in recent years and many interesting new methodologies have been reported. The purpose of this review is to give the reader a tour of the methods that have emerged in the last few years so one can appreciate the myriad of different metals and reagents that can accomplish the oxyamination of alkenes. There are still many challenges to be overcome and, herein, we also outline the areas that are ripe for further development and which bode well for the future.

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“…Dagegen war für Glucale mit einer Sulfamoylgruppe am C3 nur eine geringere Stereokontrolle möglich. Darüber hinaus kann die Chemoselektivität der Reaktion, wie im Fall der Carbamate, durch die Einführung von elektronenziehenden Schutzgruppen verbessert werden: Ein C4‐Sulfamoylglucal‐Analogon zu 11 ging eine allylische C‐H‐Insertion an C3 ein, nachdem diese Position durch eine elektronenreichere O‐Silylgruppe substituiert wurde 35b…”

Section: Katalytische Difunktionalisierung Von Alkenenunclassified

Nitren‐Chemie in der organischen Synthese: noch in den Kinderschuhen?

2012

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Stickstoff zählt zu den lebenswichtigen Elementen. Daher wird der Entwicklung von Synthesemethoden zur Einführung dieses Elements in Moleküle besondere Beachtung geschenkt. Nachdem Nitrene seit langem als sehr reaktive, doch unselektive Spezies bekannt waren, konnten sie kürzlich auch zur Bildung von C‐N‐Bindungen eingesetzt werden. Nun sind metallkatalysierte Methoden für die Synthese von Aminen durch Aziridierung von Alkenen oder C‐H‐Aminierung von Alkanen verfügbar. Die hier beschriebenen Ergebnisse zeigen, dass die Nitren‐Chemie für einen größeren Anwendungsbereich in der Synthese nutzbar wird und nicht auf diese beiden Reaktionen beschränkt bleibt.

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Highly stereoselective synthesis of aminoglycosides via rhodium-catalyzed and substrate-controlled aziridination of glycals

Cited by 48 publications

References 23 publications

Mechanistic Insights into the Substrate‐Controlled Stereochemistry of Glycals in One‐Pot Rhodium‐Catalyzed Aziridination and Aziridine Ring Opening

Mechanistic Insights into the Substrate‐Controlled Stereochemistry of Glycals in One‐Pot Rhodium‐Catalyzed Aziridination and Aziridine Ring Opening

Recent Developments in Methodology for the Direct Oxyamination of Olefins

Nitren‐Chemie in der organischen Synthese: noch in den Kinderschuhen?

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