Enantioselective Iridium‐Catalyzed Allylation of Acetylenic Ketones via 2‐Propanol‐Mediated Reductive Coupling of Allyl Acetate: C14‐C23 of Pladienolide D

Abstract

Highly enantioselective catalytic reductive coupling of allyl acetate with acetylenic ketones occurs in a chemoselective manner in the presence of aliphatic or aromatic ketones. This method was used to construct C14‐C23 of pladienolide D in half the steps previously required.

Total Syntheses of Pladienolide-Derived Spliceosome Modulators

“…Yoo and Krische’s synthesis is based on the parallel preparation of small fragments 57 , 105 , 106 , and 107 ( Scheme 19 ). Preparation of 105 commenced with the Sharpless asymmetric epoxidation of allylic alcohol 108 [ 76 ]. Regioselective epoxidation of more substituted alkenes in 108 afforded the highly enantiomerically rich epoxide 109 (dr = 20:1, 95% ee ), which was regioselectively opened by the dienolate 47 to afford 110 after one-pot acetylation.…”

Preise der American Chemical Society 2020

“…Krisches Gruppe ist führend auf dem Gebiet reduktiver C‐C‐Kupplungen mit π‐ungesättigten Substraten. In einer Angewandte‐Chemie ‐Zuschrift stellten sie eine enantioselektive Allylierung von Inonen vor, und sie steuerten einen Minireview über enantioselektive Carbonylpropargylierungen zum “10th Anniversary Issue of ChemCatChem ” bei. Krische ist Mitglied des internationalen Beirats von ChemCatChem .…”

American Chemical Society National Awards 2020

“…Krische's group has pioneered reductive C−C couplings with abundant π‐unsaturated feedstocks. In a Communication in Angewandte Chemie , they presented an enantioselective allylation of acetylenic ketones, and they contributed a Minireview on enantioselective carbonyl propargylation to the 10th Anniversary Issue of ChemCatChem . Krische is on the International Advisory Board of ChemCatChem .…”