Among the available methods to increase the molecular complexity, sigmatropic rearrangements occupy a distinct position in organic synthesis. Despite being known for over a century sigmatropic rearrangement reactions of ylides via carbene transfer reaction have only recently come of age. Most of the ylide mediated rearrangement processes involve rupture of a σ‐bond and formation of a new bond between π‐bond and negatively charged atom followed by simultaneous redistribution of π‐electrons. This minireview describes the advances in this research area made in recent years, which now opens up metal‐catalyzed enantioselective sigmatropic rearrangement reactions, metal‐free photochemical rearrangement reactions and novel reaction pathways that can be accessed via ylide intermediates.

Hexafluoroisopropanol is typically considered as an unreactive solvent and not as a reagent in organic synthesis. Herein, we report on a mild and efficient photochemical reaction of aryl diazoacetates with hexafluoroisopropanol that enables, under stoichiometric reaction conditions, the synthesis of fluorinated ethers in excellent yield. Mechanistic studies indicate there is a preorganization of hexafluoroisopropanol and the diazoalkane acts as an unreactive hydrogen‐bonding complex. Only after photoexcitation does this complex undergo a protonation‐substitution reaction to the reaction product. Investigations on the applicability of this photochemical transformation show that a broad variety of acidic alcohols can be subjected to this transformation and thus demonstrate the feasibility of this concept for O‐H functionalization reactions (54 examples, up to 98 % yield).

The reaction mechanism of oxygen and sulfur ylide mediated rearrangements is even today a matter of debate. In this report, we describe ring expansion reactions of oxetane and thietane heterocycles that allow probing the underlying reaction mechanism under metal-free, photochemical conditions. This ring expansion proves highly efficient and allows the synthesis of tetrahydrofuran and thiolane heterocycles under mild and operationally simple reaction conditions. These studies reveal marked differences in the stereoselectivity of the ring expansion of oxygen or sulfur ylides, which were further investigated computationally. DFT calculations show that carbenes react under ylide formation and that the corresponding ring expansion reactions proceed via a diradical pathway. The different bond lengths in free oxygen or sulfur ylide intermediates cause the distinctive stereochemical outcome.

Controlling the reactivity of carbene intermediates is a key parameter in the development of selective carbene transfer reactions and is usually achieved by metal complexes via singlet metal‐carbene intermediates. In this combined experimental and computational studies, we show that the reactivity of free diaryl carbenes can be controlled by the electronic properties of the substituents without the need of external additives. The introduction of electron‐donating and ‐withdrawing groups results in a significant perturbation of singlet triplet energy splitting of the diaryl carbene intermediate and of activation energies of consecutive carbene transfer reactions. This strategy now overcomes a long‐standing paradigm in the reactivity of diaryl carbenes and allows the realization of highly chemoselective carbene transfer reactions with alkynes. We could show that free diaryl carbenes can be readily accessed via photolysis of the corresponding diazo compounds and that these carbenes can undergo highly chemoselective cyclopropenation, cascade, or C−H functionalization reactions. Experimental and theoretical mechanistic analyses confirm the participation of different carbene spin states and rationalize for the observed reactivity.

The photolysis of diazoalkanes is a timely strategy to conduct carbene‐transfer reactions under mild and metal‐free reaction conditions, and has developed as an important alternative to conventional metal‐catalyzed carbene‐transfer reactions. One of the major limitations lies within the rapidly occurring side reaction of the carbene intermediate with remaining diazoalkane molecules that result in the use of an excess of the reaction partner and thus impacts on the reaction efficiency. Herein, we describe a protocol that takes advantage of the in situ generation of donor–acceptor diazoalkanes by Bamford–Stevens reaction. Following this strategy, the concentration of the diazoalkane reaction partner can be minimized to reduce unwanted side reactions and to now conduct photochemical carbene transfer reactions under stoichiometric reaction conditions. We have explored this approach in the C−H and N−H functionalization and cyclopropanation reaction of N‐heterocycles and could demonstrate the applicability of this method in 51 examples.