Importance of favourable non-covalent contacts in the stereoselective synthesis of tetrasubstituted chromanones
Importance of favourable non-covalent contacts in the stereoselective synthesis of tetrasubstituted chromanones
复制标题
有利的非共价接触在四取代色满酮立体选择性合成中的重要性
DOI：
10.1039/d2qo00090c
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发表时间：
2022
影响因子：
5.4
通讯作者：
Wheeler, Steven E.
中科院分区：
文献类型：
--
作者：
Andreola, Laura R.;Wheeler, Steven E.
最近报道的钯催化芳基硼酸偶联加成到2取代的铬的自动过渡态（TS）结构计算（D. Baek， H. Ryu， J. Y. Ryu， J. Lee， B. M. Stoltz和S. Hong, Chem.）科学。化学学报，2020,11,4602-4607)揭示了吡啶-二氢异喹啉（PyDHIQ）配体上关键立体分化苄基的意外构象。详细分析表明，立体选择性主要是由苯基与底物之间有利的非共价接触决定的，并结合初级TS结构中的扭转应变导致次要立体异构体。这一发现应该为PyDHIQ和相关配体在其他立体选择转化中的进一步使用和分析提供信息。
Automated transition state (TS) structure computations for a recently reported Pd-catalysed conjugated addition of arylboronic acids to 2-substituted chromones (D. Baek, H. Ryu, J. Y. Ryu, J. Lee, B. M. Stoltz and S. Hong, Chem. Sci., 2020, 11, 4602–4607) reveal unexpected conformations of the key stereodifferentiating benzyl group on the pyridine-dihydroisoquinoline (PyDHIQ) ligand. Detailed analysis shows that stereoselectivity is determined primarily by favourable non-covalent contacts between this benzyl group and the substrates, combined with torsional strain in the primary TS structure leading to the minor stereoisomer. This finding should inform further use and analysis of PyDHIQ and related ligands in other stereoselective transformations.