Arylboronic Acid Catalyzed C-Alkylation and Allylation Reactions Using Benzylic Alcohols

Abstract

The arylboronic acid catalyzed dehydrative C-alkylation of 1,3-diketones and 1,3-ketoesters using secondary benzylic alcohols as the electrophile is reported, forming new C–C bonds (19 examples, up to 98% yield) with the release of water as the only byproduct. The process is also applicable to the allylation of benzylic alcohols using allyltrimethylsilane as the nucleophile (12 examples, up to 96% yield).

Zirconium-catalysed direct substitution of alcohols: enhancing the selectivity by kinetic analysis

“…[66][67][68] In addition, symmetric side-products are recurrently observed for such unsymmetrical intermolecular etherification protocols and can significantly decrease the yields of these processes. 21,[69][70][71][72] During the last decades, modern and user-friendly methodologies have been developed for intuitive visual kinetic analysis of organic reactions, known as Reaction Progress Kinetic Analysis (RPKA) and Variable Time Normalization Analysis (VTNA). [73][74][75][76][77][78] These methodologies enable facile extraction of kinetic data by utilization of full reaction profiles for a minimal number of experiments under synthetically relevant conditions.…”

Microwave‐Assisted Condensation of Benzylic Alcohols and Alkynes Promoted by Zinc Halides: Concise Access to Alkenyl Halides

“…To inspect the versatility of the process, first, synthesized the secondary benzylic alcohols 1 a‐i according to the previous literature reports [36–41] or commercially purchased; subsequently, subjected them to the optimized reaction conditions with the terminal acetylenes (Table 1, Entry 6). Now, these alcohols 1 a – i were treated with different terminal alkynes 2 a – h under established microwave heating conditions (i. e., Table 1, entry 6).…”

Direct activation of alcohols via perrhenate ester formation for an intramolecular dehydrative Friedel–Crafts reaction

“…The direct application of alcohols as alkylating reagents is attracting increasing attention from the academic society and many innovative activation modes for alcohols have been invented. 5–9 Re 2 O 7 -mediated direct activation of reactive alcohols was realized when stable carbenium ions were formed (Fig. 1B); 10,11 however, debates exist over whether these reactions proceed through perrhenate ester formation or through Brønsted acid-catalyzed dehydration.…”