Broadly effective enantioselective Diels-Alder reactions of 1-amino-substituted-1,3-butadienes

[reaction: see text] A broad range of substituted 1-amino-1,3-butadienes undergo enantioselective Diels-Alder reactions with methacrolein in the presence of 5 mol % of Cr(III)-salen complex 1. The reactions are carried out conveniently, at room temperature, and they afford the cycloadducts in high yields and excellent ee's.     

Rapid synthesis of the N-methylwelwitindolinone skeleton

An efficient, convergent synthesis of the core bicyclo[4.3.1]decane ring system of welwitindolinones is described. Key steps in the synthesis include an intramolecular palladium-catalyzed enolate arylation reaction to create the desired bicyclic skeleton and a Curtius rearrangement to install the bridgehead isocyanate unit. [reaction: see text]     

On Toughness and Hamiltonicity of 2K2‐Free Graphs

The toughness of a (noncomplete) graph G is the minimum value of t for which there is a vertex cut A whose removal yields components. Determining toughness is an NP‐hard problem for general input graphs. The toughness conjecture of Chvátal, which states that there exists a constant t such that every graph on at least three vertices with toughness at least t is hamiltonian, is still open for general graphs. We extend some known toughness results for split graphs to the more general class of 2K₂‐free graphs, that is, graphs that do not contain two vertex‐disjoint edges as an induced subgraph. We prove that the problem of determining toughness is polynomially solvable and that Chvátal's toughness conjecture is true for 2K₂‐free graphs.     

Mixing of the Glauber dynamics for the ferromagnetic Potts model

We present several results on the mixing time of the Glauber dynamics for sampling from the Gibbs distribution in the ferromagnetic Potts model. At a fixed temperature and interaction strength, we study the interplay between the maximum degree (Δ) of the underlying graph and the number of colours or spins (q) in determining whether the dynamics mixes rapidly or not. We find a lower bound L on the number of colours such that Glauber dynamics is rapidly mixing if at least L colours are used. We give a closely‐matching upper bound U on the number of colours such that with probability that tends to 1, the Glauber dynamics mixes slowly on random Δ‐regular graphs when at most U colours are used. We show that our bounds can be improved if we restrict attention to certain types of graphs of maximum degree Δ, e.g. toroidal grids for Δ = 4. © 2014 Wiley Periodicals, Inc. Random Struct. Alg., 48, 21–52, 2016     

A unified route to the welwitindolinone alkaloids: total syntheses of (-)-N-methylwelwitindolinone C isothiocyanate, (-)-N-methylwelwitindolinone C isonitrile, and (-)-3-hydroxy-N-methylwelwitindolinone C isothiocyanate

As part of a comprehensive strategy to the welwitindolinone alkaloids possessing a bicyclo[4.3.1]decane core, we report herein concise asymmetric total syntheses of (-)-N-methylwelwitindolinone C isothiocyanate (2a), (-)-N-methylwelwitindolinone C isonitrile (2b), and (-)-3-hydroxy-N-methylwelwitindolinone C isothiocyanate (3a) from a common tetracyclic intermediate. The crucial vinyl chloride moiety was installed through electrophilic chlorination of a hydrazone, but only after adjustment of reactivity to circumvent a facile skeletal rearrangement. Selective desulfurization and oxidation of 2a provided access to 2b and 3a, respectively. Notably, this work provides corrected (1)H and (13)C NMR spectral data for 3a.     

Palladium-catalyzed C3-benzylation of indoles

A general method for regioselective C3-benzylation of indoles has been developed. Various 3-substituted indoles and benzyl methyl carbonates with different electronic properties react under mild conditions to afford a diverse range of 3-benzylindolenine products in good yields.     

Thermolytic removal of t-butyloxycarbonyl (BOC) protecting group on indoles and pyrroles

The t-Butyloxycarbonyl (BOC) group on indoles and pyrroles can be removed cleanly and in high yield by simple thermolysis: no acid, no base, no solvent is required.     

Synthesis of C-15 vindoline analogues by palladium-catalyzed cross-coupling reactions

Described are general protocols for the rapid construction of various C-15-substituted analogues of vindoline using palladium-catalyzed cross-coupling reactions. The required bromo- and iodovindolines were prepared in high yield by the reaction of vindoline with N-bromosuccinimide or N-iodosuccinimide, respectively. The study not only led to the preparation of a number of structurally novel vindoline analogues but also opens the door to new strategies for the synthesis of vinblastine, vincristine, and related anticancer agents. Also described is the conversion of ent-tabersonine to ent-vindoline.