The unprecedented application of unmodified aldehydes as nucleophilic donors in direct catalytic asymmetric Mannich-type reactions is disclosed in a full account. Our efforts in broadening the applicability of chiral pyrrolidine-based catalysts in direct asymmetric Mannich-type reactions led to the highly diastereo- and enantioselective and concise synthesis of functionalized alpha- and beta-am...

The development of a direct catalytic asymmetric Mannich reaction is shown and its potential demonstrated by the synthesis of optically active lactones via 4-hydroxyglutamic acid ester derivatives. The catalytic asymmetric Mannich reaction of carbonyl compounds with α-imino esters [Eq. (1); Ts = p-toluenesulfonyl] gives good yields and diastereoselectivities, as well as excellent enantioselecti...

A catalytic asymmetric nitro-Mannich (aza-Henry) reaction with rare earth metal/alkali metal heterobimetallic catalysts is described. A Yb/K heterobimetallic catalyst assembled by an amide-based ligand promoted the asymmetric nitro-Mannich reaction to afford enantioenriched anti-b-nitroamines in up to 86% ee. Facile reduction of the nitro functionality allowed for efficient access to optically ...

Intermolecular couplings of simple building blocks using catalytic, stereoselective cross-Mannich reactions followed by intramolecular functional group-pairing reactions of easily accessed variants of the Mannich products are explored as a route to skeletally diverse small molecules. The synthetic pathway yields products having 12 different skeletons using only three steps and has the potential...

The solid state structure of 1-((1H-benzotriazol-1-yl)methyl)naphthalen-2-ol, C17H13N3O, shows that this Mannich base crystallizes forming intermolecular N...HO hydrogen bonds, rather than intramolecular ones. Factors contributing to this choice of hydrogen-bonding mode are discussed. The compound crystallizes in the monoclinic system, P2(1)/c space group, with lattice constants: a = 11.7934(9)...

An asymmetric Mannich reaction of phenylacetate thioesters and sulfonylimines using cinchona alkaloid-based amino (thio)urea catalysts is reported that employs proximity-assisted soft enolization. This approach to enolization is based on the cooperative action of a carbonyl-activating hydrogen bonding (thio)urea moiety and an amine base contained within a single catalytic entity to facilitate i...

The title ferrocene-containing Mannich base, [Fe(C(5)H(5))(C(16)H(16)NO(2))], crystallizes with two independent mol-ecules (A and B) in the asymmetric unit. Mol-ecules A and B have similar conformations. The dihedral angles between the best planes of the benzene and substituted cyclo-penta-dienyl rings are 88.59 (9) and 84.39 (10)° in A and B, respectively. In the crystal, the independent mol-e...

A direct β-coupling of cyclic ketones with imines has been accomplished via the synergistic combination of photoredox catalysis and organocatalysis. Transient β-enaminyl radicals derived from ketones via enamine and oxidative photoredox catalysis readily combine with persistent α-amino radicals in a highly selective hetero radical-radical coupling. This novel pathway to γ-aminoketones is predic...