Mechanism and Stereoselectivity of the BINOL-Catalyzed Allylboration of Skatoles

Density functional theory calculations have been performed to investigate the binaphthol-catalyzed allylboration of skatoles. The high stereoselectivity observed for the reaction is reproduced well by the calculations and was found to be mainly a result of steric repulsions in the corresponding Zimmerman–Traxler transition states. The role of the additive MeOH in enhancing the stereoselectivity was also investigated and is suggested to promote the formation of less reactive allylboronic ester intermediates, thereby suppressing the formation of allylboroxine species, which undergo the facile racemic background reaction

Scalable, Chromatography-Free Synthesis of Alkyl-Tethered Pyrene-Based Materials. Application to First-Generation “Archipelago Model” Asphaltene Compounds

In this paper, we report a highly efficient, scalable approach to the total synthesis of conformationally unrestricted, electronically isolated arrays of alkyl-tethered polycyclic aromatic chromophores. This new class of modular molecules consists of polycyclic aromatic “islands” comprising significant structural fragments present in unrefined heavy petroleum, tethered together by short saturated alkyl chains, as represented in the “archipelago model” of asphaltene structure. The most highly branched archipelago compounds reported here share an architecture with first-generation dendrimeric constructs, making the convergent, chromatography-free synthesis described herein particularly attractive for further extensions in scope and applications to materials chemistry. The syntheses are efficient, selective, and readily adaptable to a multigram scale, requiring only inexpensive, “earth-abundant” transition-metal catalysts for cross-coupling reactions and extraction and fractional crystallization for purification. This approach avoids typical limitations in cost, scale, and operational practicality. All of the archipelago compounds and synthetic intermediates have been fully characterized spectroscopically and analytically. The solid-state structure of one archipelago model compound has been determined by X-ray crystallography