a b s t r a c tThe one-pot reaction of aldehydes, triacetic acid lactone, and Hantzsch 1,4-dihydropyridine affords 3-alkyl pyrones via a reductive alkylation strategy.

Automation of chemical reactions through tools such as Rxn Rover in research and development is an enabling technology to reduce cost and waste management in technology transformations towards renewable feedstocks and energy in the chemical industry.

A novel diastereoselective, Lewis acid catalyzed 1,6-difunctionalization of galactose and mannose derivatives has been developed in one pot, via sequential nucleophile additions. Our studies point to the formation of a 3,6-anhydrosugar intermediate as key to the 1,6-site-selectivity. Starting material-specific reactivity occurs when competitive ring-opening C–O cleavage is possible, owed to basicity and stereoelectronic stabilization differences. Lastly, Mayr nucleophilicity parameter values helped predict which reaction conditions would be most suitable for specific nucleophiles.

The ambi-valent character of the P–I bond in iodophosphonium complexes ensures that it can be electrophilic at either P or I. Herein, we use an ensemble of computational tools and methodologies to probe the nature of this ambi-valent bond. Geometric and atomic electron population analyses yielded strong trends between the electron donating ability of the phosphine and the strength and polarity of the P–I bond. Quasi-atomic orbital analysis demonstrated the near homo-polarity of the P–I bond, and energy decomposition analysis calculations demonstrated the ability to tune the polarization of the bond with only mild changes in secondary structural features. Finally, the ambi-valent nature of the P–I bond was demonstrated to follow hard–soft considerations in reactions with nucleophiles, with harder nucleophiles preferentially forming products of addition to P and softer nucleophiles to I.