Synthesis and Structural Characterization of a New Class of Strong Chiral Brønsted Acids: 1,1′‐Binaphthyl‐2,2′‐bis(sulfuryl)imides (JINGLEs)

Abstract

We herein present the first synthesis of 1,1′‐binaphthyl‐2,2′‐bis(sulfuryl)imides (JINGLEs). This new class of chiral Brønsted acids was synthesized in one step from the corresponding BINOLs and imidobis(sulfuryl chloride). A total of six enantiopure 1,1′‐binaphthyl‐2,2′‐bis(sulfuryl)imides, carrying different 3,3′‐substituents, were synthesized and characterized, inter alia, by X‐ray crystallography.

On the Acidity and Reactivity of Highly Effective Chiral Brønsted Acid Catalysts: Establishment of an Acidity Scale

“…Furthermore, Brønsted acid organocatalysts based on bis(sulfonyl)imides were introduced by Berkessel et al. (JINGLE, Scheme )8a and Giernoth and co‐workers (BINBAM) 8b…”

Modulation der Acidität – hoch acide Brønsted‐Säuren in der asymmetrischen Katalyse

“…[9] Eine erst jüngst entwickelte Klasse starker chiraler Brønsted-Säuren sind die ebenfalls von Binol abgeleiteten Bis(sulfuryl)imide (Jingles) mit einem geschätzten pK a -Wert in Acetonitril von 5 (Abbildung 2, rechts). [9,10] In naher Zukunft sind weitere interessante Entwicklungen in diesem Forschungsbereich zu erwarten. Abbildung 3 fasst alle innerhalb dieses Kurzaufsatzes diskutierten BPs und NTPAs sowie ihre Derivate zusammen.…”

Chiral Anion Directed Asymmetric Carbocation‐Catalyzed Diels–Alder Reactions

“…General: All reactions were performed in pre‐dried solvents under a nitrogen atmosphere. Imidobis(sulfuryl chloride) was prepared in accordance with literature procedures 13,16. The 1 H and 13 C NMR spectra were recorded at 500 or 400 MHz and 125 MHz, respectively.…”

“…Here we present our attempts toward this goal based on asymmetric counter‐anion directed catalysis (Scheme ). We based our strategy on the in situ formation of a contact trityl cation/chiral anion pair from corresponding trityl chloride TrCl 2 and the silver or sodium salt of chiral phosphates 3 ,10 phosphoric amides 4 ,11 bis(sulfonyl)amide 5 ,12 or bis(sulfuryl)amide 6 13 (Figure 1 and Figure 2). We anticipated that the chiral ion pair formed would be in equilibrium with the inactive covalent bound Tr‐anion species (Scheme ).…”