Self‐promoted glycosylations have generally not received much attention, despite having the advantages of being easy to perform and often highly stereoselective. This account covers the work done in this field and the mechanistic aspects of self‐promoted glycosylations are discussed, with a main focus on the stereoselectivity of the reactions. Most self‐promoted glycosylations utilize trichloroacetimidate donors, but examples of self‐promoted reactions with other donors have been described and will be discussed. Self‐promoted glycosylation strategies can provide a basis for new stereoselective glycosylation methodologies.
A new way of performing reaction optimization within carbohydrate chemistry is presented. This is done by performing closed-loop optimization of regioselective benzoylation of unprotected glycosides using Bayesian optimization. Both 6-O-monobenzoylations and...
A new way of performing reaction optimization within carbohydrate chemistry is presented. This is done by performing closed-loop optimization of regioselective benzoylation of unprotected glycosides using Bayesian optimization. Both 6-O- monobenzoylations and 3,6-O-dibenzoylations of three different monosaccharides are optimized. A novel transfer learning approach, where data from previous optimizations of different substrates is used to speed up the optimizations, has also been developed. The optimal conditions found by the Bayesian Optimization algorithm provide new insight into substrate specificity, as the conditions found are significantly different. In most cases, the optimal conditions include Et3N and benzoic anhydride, a new reagent combination for these reactions, discovered by the algorithm, demonstrating the power of this concept to widen the chemical space. Further, the developed procedures include ambient conditions and short reaction times.
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