Development of chiral inductive diastereoselective dehydrative nucleophilic substitutions of diastereomixtures of diarylmethanols catalyzed by Lewis acids

2022 Fiscal Year Final Research Report

• Project/Area Number: 20K05495
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 33020:Synthetic organic chemistry-related
• Research Institution: Shimane University
• Principal Investigator: NAKATA Kenya 島根大学, 学術研究院環境システム科学系, 准教授 (00434019)
• Project Period (FY): 2020-04-01 – 2023-03-31
• Keywords: 求核置換反応 / カルボカチオン / ルイス酸 / ジアステレオ選択性 / 不斉補助基 / 合成手法

Outline of Final Research Achievements

We have attempted to apply a variety of nucleophiles to the Lewis acid-catalyzed dehydration-type nucleophilic substitution reaction of alcohols as substrates, in order to establish a new method for supplying novel compounds. As a results, we have developed a Lewis acid-catalyzed sulfamidation of benzylic alcohols using nucleophilic substitution reactions. Next, we have successfully established diastereodivergnet sulfamidation of diastereomixtures of alcohols with chiral auxiliary using different Lewis acid catalysts. Furthermore, an interesting phenomenon was observed in which the diastereoselectivity of the reaction was reversed depending on the equivalent amount of Lewis acid catalyst used. In conclusion, we have extended the Lewis acid catalyzed nucleophilic reactions of alcohols to asymmetric versions and succeeded in creating new transformation reactions.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

不斉補助基による立体化学の制御法は，光学活性化合物を効率的に与える信頼性のある手法として知られており，現在までに多くの反応が報告されている。しかし，アルコールの直接的な脱水型求核置換反応と不斉補助基を組み合わせた反応は，全く試みられていない研究領域である。従来報告例のない反応を新たに開発し，その反応機構を解明していくことは，今後の反応設計の指針となり，当該領域の発展に大きく寄与すると考えられ，我々がその役割を果たしていくつもりである。