Esterification in an aqueous micellar medium is catalyzed by a commercially available lipase in the absence of any co-factors. The presence of only 2 wt% designer surfactant, TPGS-750-M, assists in a 100% selective enzymatic process in which only primary alcohols participate (in a 1 : 1 ratio with carboxylic acid). An unexpected finding is also disclosed where the simple additive, PhCF₃ (1 equiv. vs. substrate), appears to significantly extend the scope of usable acid/alcohol combinations. Taken together, several chemo- and bio-catalyzed 1-pot, multi-step reactions can now be performed in water.

Bio-catalytic reactions involving ene-reductases (EREDs) in tandem with chemo-catalysis in water can be greatly enhanced by the presence of nanomicelles derived from the surfactant TPGS-750-M.

Surfactant-enabled asymmetric ATA-catalyzed reductive aminations in aqueous buffered media are described, representative of the enhanced levels of conversion made possible by the presence of a nonionic surfactant in the water, thereby enabling 1-pot chemoenzymatic catalysis. Several applications are described highlighting these modified conditions that involve both biocatalysis and chemocatalysis that are environmentally responsible, indicative of the possibilities using chemistry in water. Also included herein is technology for converting a racemic benzylic alcohol to a nonracemic primary amine, and an especially efficient synthesis of the pharmaceutical (S)-rivastigmine.

A practical generalisable procedure to synthesize hydroxymethylene H-bisphosphinates has been optimised. Unlike previous reports, numerous alkyl (including an alendronate bisphosphinate analogue) or (hetero)aryl compounds were rapidly obtained in satisfactory to excellent yields. A side product could have been identified as a phosphino-phosphonate isomer and plausible mechanistic pathways are proposed here. Moreover to check the literature data, a pK_a value study was also performed.

Enamine catalysis is a widespread activation mode in the field of organocatalysis and is often encountered in bifunctional organocatalysts. We previously described H‐Pro‐Pro‐pAla‐OMe as a bifunctional catalyst for Michael addition between aldehydes and aromatic nitroalkenes. Considering that opposite selectivities were observed when compared to H‐Pro‐Pro‐Glu‐NH₂, an analogue described by Wennemers, the activation mode of H‐Pro‐Pro‐pAla‐OMe was investigated through kinetic, linear effect studies, NMR analyses, and structural modifications. It appeared that only one bifunctional catalyst was involved in the catalytic cycle, by activating aldehyde through an (E)‐enamine and nitroalkene through an acidic interaction. A restrained tripeptide structure was optimal in terms of distance and rigidity for better selectivities and fast reaction rates. Transition‐state modeling unveiled the particular selectivity of this phosphonopeptide.