There is a growing need in organic synthesis for efficient methodologies for the asymmetric synthesis of quaternary carbon centres. One of the most attractive and straightforward methods focuses on the use of asymmetric catalysis for the addition of various types of nucleophiles on prochiral ketones and ketimines. A view of the literature from this growing area of research will be presented in this review, with an emphasis on the pioneer works and milestones brought by the main players in this field.

This literature review focuses on the recent advances in the asymmetric hydrosilylation of ketones and imines. New catalyst systems based on various transition metals, such as rhodium, titanium, zinc, copper and tin, combined with classical or new ligand structures, are presented. These systems lead to very effective and selective protocols for the reduction of prochiral ketones, imines and electrophilic double bonds. 1 Introduction 2 Rhodium-Based Catalysts 3 Titanium-Based Catalysts 3.1 Hydrosilylation of Ketones 3.2 Hydrosilylation of Imines 4 Zinc-Based Catalysts 5 Copper-Based catalysts 5.1 Asymmetric Hydrosilylation of Electrophilic Double Bonds 5.2 Asymmetric Hydrosilylation of Ketones and Imines 6 Conclusions

Lactate exchange between glycolytic and oxidative cancer cells is proposed to optimize tumor growth. Blocking lactate uptake through monocarboxylate transporter 1 (MCT1) represents an attractive therapeutic strategy but may stimulate glucose consumption by oxidative cancer cells. We report here that inhibition of mitochondrial pyruvate carrier (MPC) activity fulfils the tasks of blocking lactate use while preventing glucose oxidative metabolism. Using in vitro ¹³C-glucose and in vivo hyperpolarized ¹³C-pyruvate, we identify 7ACC2 as a potent inhibitor of mitochondrial pyruvate transport which consecutively blocks extracellular lactate uptake by promoting intracellular pyruvate accumulation. Also, while in spheroids MCT1 inhibition leads to cytostatic effects, MPC activity inhibition induces cytotoxic effects together with glycolysis stimulation and uncompensated inhibition of mitochondrial respiration. Hypoxia reduction obtained with 7ACC2 is further shown to sensitize tumor xenografts to radiotherapy. This study positions MPC as a control point for lactate metabolism and expands on the anticancer potential of MPC inhibition.