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使用醇作为试剂，高立体选择性保留地直接催化 α-氨基酸酯和酰胺的 N-烷基化反应。

Direct Catalytic N-Alkylation of α-Amino Acid Esters and Amides Using Alcohols with High Retention of Stereochemistry.

机构信息

Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen (The, Netherlands.

Institute for Chemistry, University of Graz, Heinrichstrasse 28/II, 8010, Graz, Austria.

出版信息

ChemSusChem. 2021 Jun 8;14(11):2303-2307. doi: 10.1002/cssc.202100373. Epub 2021 May 7.

DOI:10.1002/cssc.202100373
PMID:33961350
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8252633/
Abstract

The direct functionalization of naturally abundant chiral scaffolds such as α-amino acid esters or amides with widely abundant alcohols, without any racemization, is a demanding transformation that is of central importance for the synthesis of bio-active compounds. Herein a robust and general method was developed for the direct N-alkylation of α-amino acid esters and amides with alcohols. This powerful ruthenium-catalyzed methodology is atom-economic, base-free, and allowed for excellent retention of stereochemical integrity. The use of diphenylphosphate as additive was crucial for significantly enhancing reactivity and product selectivity. Notably, the only by-product was water and both substrates could be potentially derived from renewable resources.

摘要

直接将天然丰富的手性骨架（如α-氨基酸酯或酰胺）与广泛存在的醇进行功能化，而不发生外消旋化，是一种具有挑战性的转化，对于生物活性化合物的合成至关重要。本文开发了一种用于α-氨基酸酯和酰胺与醇的直接 N-烷基化的稳健且通用的方法。这种强大的钌催化方法具有原子经济性、无碱和出色的立体化学完整性保留。使用磷酸二苯酯作为添加剂对于显著提高反应性和产物选择性至关重要。值得注意的是，唯一的副产物是水，并且两种底物都可能来自可再生资源。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f68/8252633/dd180edfe56d/CSSC-14-2303-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f68/8252633/cf656b8c8f4b/CSSC-14-2303-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f68/8252633/7b4356c1e308/CSSC-14-2303-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f68/8252633/e75bb3995c50/CSSC-14-2303-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f68/8252633/a3d94f4443e5/CSSC-14-2303-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f68/8252633/dd180edfe56d/CSSC-14-2303-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f68/8252633/cf656b8c8f4b/CSSC-14-2303-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f68/8252633/7b4356c1e308/CSSC-14-2303-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f68/8252633/e75bb3995c50/CSSC-14-2303-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f68/8252633/a3d94f4443e5/CSSC-14-2303-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3f68/8252633/dd180edfe56d/CSSC-14-2303-g005.jpg

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