20464-36-2

The development of a multicolor mechanochromic polymer/silica composite is achieved by using two distinct types of mechanochromophores. The multicolor mechanochromism of the composite containing diarylbibenzofuranone in silica-rich domains and naphthopyran in the polymer-rich domain is observed. The obtained composite shows blue, green, and orange colors according to the intensity of applied mechanical stimuli, solvent addition, and lapse of time. This unique multicolor mechanochromic behavior is evaluated by solid-state UV-vis absorption spectroscopy, ab initio steered molecular dynamics simulations, and computed minimum energy paths on force-modified potential energy surfaces. The unique mechanochromism is attributed to the difference in properties, activated colors, and domain locations between the two mechanochromophores.

Herein, we report an efficient isomerization-transfer hydrogenation reaction sequence based on a cobalt pincer catalyst (1 mol %), which allows the synthesis of a series of anti-Markovnikov alcohols from terminal and internal epoxides under mild reaction conditions (≤55 °C, 8 h) at low catalyst loading. The reaction proceeds by Lewis acid (3 mol % Er(OTf)3)-catalyzed epoxide isomerization and subsequent cobalt-catalyzed transfer hydrogenation using ammonia borane as the hydrogen source. The general applicability of this methodology is highlighted by the synthesis of 43 alcohols from epoxides. A variety of terminal (23 examples) and 1,2-disubstituted internal epoxides (14 examples) bearing different functional groups are converted to the desired anti-Markovnikov alcohols in excellent selectivity and yields of up to 98%. For selected examples, it is shown that the reaction can be performed on a preparative scale up to 50 mmol. Notably, the isomerization step proceeds via the most stable carbocation. Thus, the regiochemistry is controlled by stereoelectronic effects. As a result, in some cases, rearrangement of the carbon framework is observed when tri-and tetra-substituted epoxides (6 examples) are converted. A variety of functional groups are tolerated under the reaction conditions even though aldehydes and ketones are also reduced to the respective alcohols under the reaction conditions. Mechanistic studies and control experiments were used to investigate the role of the Lewis acid in the reaction. Besides acting as the catalyst for the epoxide isomerization, the Lewis acid was found to facilitate the dehydrogenation of the hydrogen donor, which enhances the rate of the transfer hydrogenation step. These experiments additionally indicate the direct transfer of hydrogen from the amine borane in the reduction step.