Insights into Substrate Self-Assisted Activation of Allylic Alcohols Guiding to Mild Allylic Substitution of Tautomerizable Heteroarenes

Abstract

A substrate self-assisted activation of allylic alcohols by tautomerizable heteroarenes via hydrogen bonding was disclosed by various NMR techniques, including variable-temperature 1 H NMR, Job plot, and 1 H NMR titration. Guided by these finding, a much milder allylic substitution of tautomerizable heteroarenes with allylic alcohols was developed, affording the target products in high yields.

Photocatalytic C–H Activation with Alcohol as a Hydrogen Atom Transfer Agent in a 9-Fluorenone Based Metal–Organic Framework

“…With the addition of 9-fluorenone, the hydroxy splitting peak chemically shifted from δ 3.00 to δ 3.21, which suggests that hydrogen bonds were formed (Figure S19). 57,58 The yield obtained with the homogeneous photocatalyst H 2 OFDC was obviously lower than that of the MOFbased photocatalyst, which could be attributed to: (1) the higher stability of the excited state of the 9-fluorenone moiety when it was fixed in the framework, (2) the stronger hydrogen bonding interaction between 9-fluorenone and 2,2,2-trichloroethanol due to confinement by the MOF channel, or (3) the stabilization of the alkoxy radical intermediate in the MOF channel.…”

Water oxidation by Brønsted acid-catalyzedin situgenerated thiol cation: dual function of the acid catalyst leading to transition metal-free substitution and addition reactions of S–S bonds

“…This interesting reaction was observed during our continuous interest in studying thioether 9 and alcohol chemistry. 10 Since the readily available disulfides are usually odorless, much lower in toxicity, and more easily storable and disposable than the corresponding smelly and toxic thiols, we envisioned a new method for the synthesis of useful thioethers starting from the advantageous disulfides and the relatively greener alcohols. 11 As shown in Table 1, the neat mixture of di(pyridin-2-yl)disulfide ( 1a ) and benzyl alcohol ( 2a ) was initially heated under air at 130 °C in the presence of a catalytic amount of NaOH, but no desired 2-pyridyl benzyl thioether ( 3aa ) was observed (entry 1).…”

Host–guest interaction-based supramolecular prodrug self-assemblies for GSH-consumption augmented chemotherapy

“…Thus, the host-guest inclusion behaviours were carefully investigated. First, in order to confirm the host-guest stoichiometry between WP [6] and Cb-BA, the Job's plot method 29 was utilized, as described in Fig. 1.…”