Most photoredox catalysts in current use are precious metal complexes or synthetically elaborate organic dyes, the cost of which can impede their application for large-scale industrial processes. We found that a combination of triphenylphosphine and sodium iodide under 456-nanometer irradiation by blue light–emitting diodes can catalyze the alkylation of silyl enol ethers by decarboxylative coupling with redox-active esters in the absence of transition metals. Deaminative alkylation using Katritzky’s N-alkylpyridinium salts and trifluoromethylation using Togni’s reagent are also demonstrated. Moreover, the phosphine/iodide-based photoredox system catalyzes Minisci-type alkylation of N-heterocycles and can operate in tandem with chiral phosphoric acids to achieve high enantioselectivity in this reaction.

Abstract. Optimistic concurrency algorithms provide good performance for parallel programs but they are extremely hard to reason about. Program logics such as concurrent separation logic and rely-guarantee reasoning can be used to verify these algorithms, but they make heavy uses of history variables which may obscure the high-level intuition underlying the design of these algorithms. In this paper, we propose a novel program logic that uses invariants on history traces to reason about optimistic concurrency algorithms. We use past tense temporal operators in our assertions to specify execution histories. Our logic supports modular program specifications with history information by providing separation over both space (program states) and time. We verify Michael's non-blocking stack algorithm and show that the intuition behind such algorithm can be naturally captured using trace invariants.

Verifying program transformations usually requires proving that the resulting program (the target) refines or is equivalent to the original one (the source). However, the refinement relation between individual sequential threads cannot be preserved in general with the presence of parallel compositions, due to instruction reordering and the different granularities of atomic operations at the source and the target. On the other hand, the refinement relation defined based on fully abstract semantics of concurrent programs assumes arbitrary parallel environments, which is too strong and cannot be satisfied by many well-known transformations.In this paper, we propose a Rely-Guarantee-based Simulation (RGSim) to verify concurrent program transformations. The relation is parametrized with constraints of the environments that the source and the target programs may compose with. It considers the interference between threads and their environments, thus is less permissive than relations over sequential programs. It is compositional w.r.t. parallel compositions as long as the constraints are satisfied. Also, RGSim does not require semantics preservation under all environments, and can incorporate the assumptions about environments made by specific program transformations in the form of rely/guarantee conditions. We use RGSim to reason about optimizations and prove atomicity of concurrent objects. We also propose a general garbage collector verification framework based on RGSim, and verify the Boehm et al. concurrent mark-sweep GC.