可调谐协同催化对映选择性Pictet-Spengler 反应与不同含氮杂环羧酸醛。
Tunable and Cooperative Catalysis for Enantioselective Pictet-Spengler Reaction with Varied Nitrogen-Containing Heterocyclic Carboxaldehydes.
机构信息
Department of Chemistry, Yale University, New Haven, CT, 06520, USA.
Synthetic Molecule Design and Development, Eli Lilly and Company, Indianapolis, IN, 46285, USA.
出版信息
Angew Chem Int Ed Engl. 2021 Nov 8;60(46):24573-24581. doi: 10.1002/anie.202109694. Epub 2021 Oct 7.
Abstract
Herein we report an organocatalytic enantioselective functionalization of heterocyclic carboxaldehydes via the Pictet-Spengler reaction. Through careful pairing of novel squaramide and Brønsted acid catalysts, our method tolerates a breadth of heterocycles, enabling preparation of a series of heterocycle conjugated β-(tetrahydro)carbolines in good yield and enantioselectivity. Careful selection of carboxylic acid co-catalyst is essential for toleration of a variety of regioisomeric heterocycles. Utility is demonstrated via the three-step stereoselective preparation of pyridine-containing analogues of potent selective estrogen receptor downregulator and U.S. FDA approved drug Tadalafil.
摘要
在此，我们报告了通过皮克特-斯彭格勒反应实现杂环羧酸醛的有机催化对映选择性功能化。通过新型手性双噁唑啉和布朗斯台德酸催化剂的精心配对，我们的方法能够容忍广泛的杂环，从而能够以良好的收率和对映选择性制备一系列杂环共轭β-（四氢）咔啉。仔细选择羧酸助催化剂对于容忍各种区域异构体杂环至关重要。通过三步立体选择性制备具有强选择性雌激素受体下调剂和美国 FDA 批准药物他达拉非的含吡啶类似物，证明了其实用性。
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