Highly Stereoselective Synthesis of Z‐Homoallylic Alcohols by Kinetic Resolution of Racemic Secondary Allyl Boronates

Abstract

Von α bis Z: Racemische α‐chirale Allylboronsäureester sind leicht aus den entsprechenden primären Allylhalogeniden zugänglich. In Gegenwart des chiralen Brønsted‐Säure‐Katalysators (R)‐TRIP reagieren sie mit Aldehyden in einer hoch effizienten kinetischen Racematspaltung unter seiten‐ und Z‐selektiver Allylierung (siehe Schema; Epin=Tetraethylethylenglycol).

Palladium‐Catalyzed Stereoselective Intramolecular Oxidative Amidation of Alkenes in the Synthesis of 1,3‐ and 1,4‐Amino Alcohols and 1,3‐Diamines

“…Significantly, the reaction can be driven either to the vinylic derivative, such as 8 (Table 1, entry 12), or to the corresponding methylketone 9 (Table 1, entry 8) by a minor modification of the reaction conditions. This strategy combines highly enantioselective organocatalysis (for the preparation of chiral starting materials16c,f) with diastereocontrolled transition metal catalysis24 and was successfully applied to a stereocontrolled synthesis of the enantiopure trisubstituted tetrahydrofuran derivative 24 that can be regarded as a C ‐nucleoside.…”