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Desymmetrization of Cyclic Sulfonimidamides by Asymmetric Allylation
Angewandte Chemie International Edition ( IF 16.6 ) Pub Date : 2024-05-09 , DOI: 10.1002/anie.202407114
David Alan Gutierrez 1 , Garrett Toth-Williams 2 , Croix Laconsay 3 , Michael Yasuda 4 , James Fettinger 2 , Michael Di Maso 5 , Jared Thomas Shaw 6
Affiliation  

Herein we report the first transition metal‐catalyzed approach to the enantioenriched synthesis of cyclic sulfonimidamides relying on commercially available palladium catalysts and ligands. High‐throughput experimentation (HTE) was employed to identify the optimal catalyst system and solvent. The method is applied to a variety of saturated and unsaturated rings and exhibits the highest selectivity for 2‐substituted allyl electrophiles. The products are further elaborated to complex, tricyclic scaffolds. DFT experiments presented herein highlight the key ligand substrate interactions leading to the high levels of enantioselectivity.

中文翻译:

环状磺酰亚胺的不对称烯丙基化去对称化

在此,我们报告了第一种依赖于市售钯催化剂和配体的过渡金属催化的环状磺酰亚胺对映体富集合成方法。采用高通量实验(HTE)来确定最佳催化剂体系和溶剂。该方法适用于各种饱和和不饱和环,并且对 2-取代烯丙基亲电子试剂表现出最高的选择性。该产品被进一步加工成复杂的三环支架。本文提出的 DFT 实验强调了导致高水平对映选择性的关键配体底物相互作用。
更新日期:2024-05-09
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