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对映异构芳香克莱森重排反应的区域选择性研究及其在5-羟基麦角硫因和波蒂罗异香豆素A全合成中的应用。

Regioselectivity Study of Contrasteric Aromatic Claisen Rearrangements and Their Utilization in the Total Syntheses of 5-Hydroxymellein and Botyroisocoumarin A.

作者信息

Tanas David K, Li Runzi, Khan Harris H, Johnson Tangela C, Brown Logan E, West Philip M, Guin Emily J, Jones Sydney E, Garci Nolan K, Canning Drew M, Ramirez Emily J, Sekhon Gurjant S, Pierce Tanner H, Ustoyev Abraham, Croatt Mitchell P

机构信息

Department of Chemistry and Biochemistry, University of North Carolina at Greensboro, Greensboro, North Carolina 27402, United States.

出版信息

J Org Chem. 2025 Sep 19;90(37):12956-12963. doi: 10.1021/acs.joc.5c01268. Epub 2025 Sep 4.

DOI:10.1021/acs.joc.5c01268
PMID:40905973
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12455646/
Abstract

In this study, we present data on the regioselectivity of aromatic Claisen rearrangements with -substituted benzenes. A variety of gentisic acid, tetralin, and -salicylamide derivatives were synthesized to test the potential of an internal base to direct the regioselectivity of -alkylation. A key mechanistic insight hinges on a reversible [3,3]-sigmatropic rearrangement step, supported by H NMR studies of the isomerization of a to crotyl group. This evidence supports the potential for the keto-enol tautomerization step of the aromatic Claisen rearrangement to be the rate-determining step. A C NMR study shows that this kinetic insight can be used to direct regioselectivity by correlating the carbonyl carbon shifts of salicylamides to the regioselectivity of the associated aromatic Claisen rearrangement. Systems with rigid, in-plane bases, especially -lactone carbonyls, are highly regioselective for the contrasteric position. The utility of this regioselectivity was used in 4-step syntheses of 5-hydroxymellein and botyroisocoumarin A.

摘要

在本研究中，我们展示了关于带有取代苯的芳香克莱森重排区域选择性的数据。合成了多种龙胆酸、四氢萘和水杨酰胺衍生物，以测试内源性碱指导烷基化区域选择性的潜力。一个关键的机理见解取决于一个可逆的[3,3] - 迁移重排步骤，这得到了α到γ巴豆基异构化的核磁共振氢谱研究的支持。该证据支持了芳香克莱森重排的酮 - 烯醇互变异构步骤有可能成为速率决定步骤。碳核磁共振研究表明，这种动力学见解可用于通过将水杨酰胺的羰基碳位移与相关芳香克莱森重排的区域选择性相关联来指导区域选择性。具有刚性平面内碱的体系，特别是γ - 内酯羰基，对反式位置具有高度的区域选择性。这种区域选择性的实用性被用于5 - 羟基水合卟啉和波替罗异香豆素A的四步合成中。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/2c7138a08921/jo5c01268_0010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/50493924df1d/jo5c01268_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/794a608f47c5/jo5c01268_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/f155842c063d/jo5c01268_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/94bcbce08c80/jo5c01268_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/456ffeae47c1/jo5c01268_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/e5ceb62b4bbb/jo5c01268_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/2df6cc4594c0/jo5c01268_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/5f5f4d2fb052/jo5c01268_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/0fc8cd7089d8/jo5c01268_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/2c7138a08921/jo5c01268_0010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/50493924df1d/jo5c01268_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/794a608f47c5/jo5c01268_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/f155842c063d/jo5c01268_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/94bcbce08c80/jo5c01268_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/456ffeae47c1/jo5c01268_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/e5ceb62b4bbb/jo5c01268_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/2df6cc4594c0/jo5c01268_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/5f5f4d2fb052/jo5c01268_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/0fc8cd7089d8/jo5c01268_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7981/12455646/2c7138a08921/jo5c01268_0010.jpg

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