Highly Enantioselective Hetero‐Diels–Alder Reaction of 1,3‐Bis(silyloxy)‐1,3‐dienes with Aldehydes Catalyzed by Chiral Disulfonimide

Abstract

Sperrig mit F: Die Titelreaktion mit 1 Mol‐% des neuen chiralen Perfluorisopropyl‐substituierten Disulfonimid‐Katalysators 1 liefert 2,6‐disubstituierte und 2,5,6‐trisubstituierte Dihydropyrone in guten Ausbeuten und mit ausgezeichneten Enantiomerenverhältnissen. Die Methode stellte ihre Nützlichkeit durch die erste enantioselektive Synthese eines wirksamen Aromatase‐Inhibitors unter Beweis.

Stronger Brønsted Acids: Recent Progress

“…List and co-workers also developed a highly enantioselective hetero-Diels−Alder reaction. 201 The reactions of Danishefsky's diene 199 with aldehydes proceeded in the presence of 1 mol % 4g at −78°C to afford multisubstituted pyranes 200 with excellent enantioselectivities (Scheme 74). In the same manner as the Danishefsky's diene, more challenging diene 201, 1,3-bis(siloxy)-1,3-dienes, participated in the reaction, and corresponding adduct 202 was obtained in excellent chemical yield with high enantioselectivity (94%, 96% ee).…”

An I(I)/I(III) Catalysis Route to the Heptafluoroisopropyl Group: A Privileged Module in Contemporary Agrochemistry

“…12 Similarly, the phenylpyrazole insecticide nicofluprole also has this core structural unit, 13 as do the broflanilides: these classes of agrochemicals have proven to be highly effective against a plenum of species including lepidopteran, coleopteran, and thysanopteran. 14 Intriguingly, this motif also features prominently in List's Diels-Alder catalyst 15 and the retinoic acid related orphan receptor RORt agonist BMT-362265 (Figure 1, lower left box). 16 This latter example underscores the potential of fluorinated tetralins in biomolecule design.…”

Expanding organofluorine chemical space: the design of chiral fluorinated isosteres enabled by I(i)/I(iii) catalysis

“…12). Although the hep-tauoroisopropyl group has become a privileged motif in agrochemical research 3,7 and currently features in drug candidates 78 and organocatalysts, 79 routes to generate a chiral analogue remained conspicuously absent. Exposing simple a-triuoromethyl styrenes (48) to uorination conditions (various amine$HF complexes, Selectuor®) in the presence of a chiral resorcinol catalyst ((R,R)-49), 80 it was possible to generate chiral products efficiently (50) and with good levels of enantioselectivity.…”