A redox-mediated molecular brake: Dynamic NMR study of 2-[2-(methylthio)phenyl] isoindolin-1-one and S-oxidized counterparts
A redox-mediated molecular brake: Dynamic NMR study of 2-[2-(methylthio)phenyl] isoindolin-1-one and S-oxidized counterparts
复制标题
DOI：
10.1021/jo034613g
复制
发表时间：
2003-10-17
影响因子：
3.6
通讯作者：
Bates, DK
中科院分区：
文献类型：
--
作者：
Jog, PV;Brown, RE;Bates, DK
通过改变2-[2-(sulfur-substituted)phenyl]isoindolin-l-ones.中硫的氧化状态来调节N-Ar“轴”的旋转速度，说明了一种基于硫化物-亚砜氧化还原循环的氧化还原介导的分子刹车甲基亚磺基(2)和甲磺酰基(3)衍生物的N-Ar转动势垒(13.6kcal mol(-1))类似于比硫化物1高5kcal摩尔(-1)。N-Ar转动速率的减慢类似于氧化时的10(4)S(-1)(280K)。相关的N-锥化/N-Ar旋转降低了N-Ar键旋转的能垒，从而降低了制动器的有效性。
A redox-mediated molecular brake based on the sulfide - sulfoxide redox cycle is illustrated by modulation of the rotation rate of an N-Ar "shaft" by varying the oxidation state of sulfur in 2-[2-(sulfur-substituted)phenyl]isoindolin-l-ones. N-Ar rotational barriers in methylsulfinyl (2) and methylsulfonyl (3) derivatives (13.6 kcal mol(-1)) are similar to5 kcal mol(-1) higher than sulfide 1. Rate reduction for N-Ar rotation is similar to10(4) s(-1) (280 K) upon oxidation. Correlated N-pyramidalization/N-Ar rotation reduces the effectiveness of the brake by decreasing the energy barrier to N-Ar bond rotation.