Chiral Organocatalyzed Intermolecular Rauhut-Currier Reaction of Nitroalkenes with Ethyl Allenoate.

An enantioselective intermolecular Rauhut-Currier (RC) reaction of nitroalkenes with ethyl allenoate has been established with quinidine-derived ß-isocupreidine. The present RC reaction afforded α-functionalized allenoates 3 in up to 94% yield with 59% enantiomeric excess (ee).

Enantio- and Diastereoselective Betti/aza-Michael Sequence: Single Operated Preparation of Chiral 1,3-Disubstituted Isoindolines.

The first enantio- and diastereoselective Betti/intramolecular aza-Michael sequence carried out using a C3-symmetric chiral trisimidazoline organocatalyst is reported. The reaction of phenols and N-tosylimines bearing a Michael acceptor moiety afforded densely functionalized 1,3-disubstituted isoindolines bearing two stereogenic centers as single diastereomers in high yields (≤93%) and excellent enantioselectivities (≤99.9%).

Multifunctional catalysis: stereoselective construction of α-methylidene-γ-lactams via an amidation/Rauhut-Currier sequence.

Mixing of acryloylchloride, dienone 2, N,N-diisopropylethylamine with chiral organocatalyst 5a, which could simultaneously act as Brønsted and Lewis base catalysts, led to a one-pot amidation/Rauhut-Currier sequence, affording α-methylidene-γ-lactams 4. Catalyst 5a could be recovered and reused by acid/base extraction without any loss of catalytic activity in the stepwise protocol.

Enantioselective organocatalytic oxidation of ketimine.

C3-Symmetric chiral trisimidazolines with m-chloroperbenzoic acid promoted the organocatalytic oxidation of N-sulfonyl ketimine. The present imidazoline catalysis produced oxaziridines bearing a tetrasubstituted carbon stereogenic center in high yields with up to 87% ee.

Phosphine-Catalyzed ß,γ-Umpolung Domino Reaction of Allenic Esters: Facile Synthesis of Tetrahydrobenzofuranones Bearing a Chiral Tetrasubstituted Stereogenic Carbon Center.

An enantio-, diastereo-, regio-, and chemoselective phosphine-catalyzed ß,γ-umpolung domino reaction of allenic esters with dienones has been developed for the first time. The designed sequence, involving oxy-Michael and Rauhut-Currier reactions, produced highly functionalized tetrahydrobenzofuranones, bearing a chiral tetrasubstituted stereogenic center, in up to 96 % ee.

An enantioselective organocatalyzed aza-Morita-Baylis-Hillman reaction of isatin-derived ketimines with acrolein.

A highly enantioselective aza-Morita-Baylis-Hillman (aza-MBH) reaction of isatin-derived ketimines with acrolein was established using ß-isocupreidine (ß-ICD) or α-isocupreine (α-ICPN) as a chiral acid-base organocatalyst. The present protocol readily furnished (S) or (R)-aza-MBH adducts with a chiral tetrasubstituted carbon stereogenic center in up to 98% ee.

Facile regio- and stereoselective metal-free synthesis of all-carbon tetrasubstituted alkenes bearing a C(sp3)-F unit via dehydroxyfluorination of Morita-Baylis-Hillman (MBH) adducts.

Highly E-selective all-carbon tetrasubstituted alkenes with a C(sp(3))-F unit have been synthesized through a dehydroxyfluorination of Morita-Baylis-Hillman (MBH) adducts which can be readily prepared from α,ß-unsaturated carbonyl compounds and α-keto esters. A variety of subsequent transformations afforded monofluoromethyl substituted heterocycles in high yields.