Photoredox Catalytic Pentafluorosulfanylative Domino Cyclization of α-Substituted Alkenes to Oxaheterocycles by Using SF.

Virtually inert sulfur hexafluoride becomes a precious pentafluorosulfanylation agent, if properly activated by photoredox catalysis, to access α-fluoro and α-alkoxy SF -compounds. This advanced protocol converts SF in the presence of alkynols as bifunctional C-C- and C-O-bond forming reagents directly into pentafluorosulfanylated oxygen-containing heterocycles in a single step from α-substituted alkenes. The proposed mechanism is supported by theoretical calculations and gives insights not only in the pentafluorosulfanylation step but also into formation of the carbon-carbon bond and is in full agreement with Baldwin's cyclization rules.

A Priori Prediction of Mass Spectrometric Product Patterns of Photoinitiated Polymerizations.

We introduce a method for the a priori prediction of mass spectra of complex poly(methyl methacrylate)s initiated by photoinitiators featuring multiple cleavage points. The method is based on permutation mathematics using multinomial coefficients to predict the probability of each poly(methyl methacrylate) species' isotopic pattern contribution to the overall mass spectrum. The method assumes a statistical behavior for the cleavage of the photoinitiator.