49764-17-2Relevant academic research and scientific papers
CgPhen-DalPhos Enables the Nickel-CatalyzedO-Arylation of Tertiary Alcohols with (Hetero)Aryl Electrophiles
Morrison, Kathleen M.,McGuire, Ryan T.,Ferguson, Michael J.,Stradiotto, Mark
, p. 10878 - 10884 (2021/09/08)
While the Ni-catalyzed cross-coupling of primary or secondary aliphatic alcohols and (hetero)aryl electrophiles is known, related cross-couplings involving tertiary aliphatic alcohols, with a broad scope, are challenging. Herein we disclose that a NiIIprecatalyst featuring the ligand CgPhen-DalPhos is unusual in its ability to promote the C-O cross-coupling of tertiary aliphatic alcohols with (hetero)aryl halides (Cl, Br, and I) or phenol derivatives (OMs and OPiv). An exploration of substrate scope and competition experiments help to shed light on the capabilities and reactivity preferences of this catalyst system.
The structure, photochemical reactivity, and photophysical properties of adamantyl X-substituted aryl ethers and a comparison with the alkyl groups, methyl, tert-butyl, and allyl
Pincock,Pincock
, p. 1237 - 1252 (2007/10/03)
The structure, photophysical properties, and photochemistry of the adamantyl aryl ethers 1 in both methanol and cyclohexane have been examined. UV absorption spectra, 13C NMR chemical shifts, X-ray structures, and Gaussian calculations (B3LYP/6-31G(d)) indicate that these ethers adopt a 90° conformer in the ground state. In contrast, fluorescence spectra, excited singlet state lifetimes, and calculations (TDDFT) indicated a 0° conformer is preferred in the first excited singlet state S1. Irradiation in either solvent results in the formation of adamantane and the corresponding phenol as the major products, both derived from radical intermediates generated by homolytic cleavage of the ether bond. The 4-cyano substituted ether 1j was the only one to form the ion-derived product, 1-methoxyadamantane (16% yield), on irradiation in methanol. Rate constants of bond cleavage for these ethers from S1 were estimated by two different methods by comparison with the unreactive anisoles 2, but the effect of substituents was too small to determine structure-reactivity correlations. The temperature dependence of the quantum yields of the fluorescence of the unsubstituted, 4-methoxy and 4-cyano derivatives of 1 and 2 were also determined. These results indicated that the activated process for 1 was mainly bond cleavage for the 4-cyano substrate whereas for 2, it was internal conversion and intersystem crossing.
