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关于-芳基--叔丁氧羰基磷酰胺酯重排为-叔丁氧羰基保护的-氨基芳基膦酸酯。

On the rearrangement of -aryl--Boc-phosphoramidates to -Boc-protected -aminoarylphosphonates.

作者信息

Kuliszewska Edyta, Hammerschmidt Friedrich

机构信息

Institute of Organic Chemistry, University of Vienna, Vienna, Austria.

出版信息

Monatsh Chem. 2018;149(1):87-98. doi: 10.1007/s00706-017-2058-x. Epub 2017 Dec 1.

DOI:10.1007/s00706-017-2058-x
PMID:29290635
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5738464/
Abstract

ABSTRACT

Various arylamines were converted in two steps to -Boc--arylphosphoramidates. LiTMP and LDA induced directed -metalation at temperatures from -78 to 0 °C. The ensuing [1,3]-migration of the phosphorus atom with its substituents from the nitrogen to the -carbanionic carbon atom gave -Boc-protected -aminoarylphosphonates. The nature of the substituent of 3-substituted phenylphosphoramidates strongly influenced the regioselectivity of phosphonate formation. A crossover experiment with a deuterated phosphoramidate proved the intramolecular course of the rearrangement. Three representative -Boc--aminoarylphosphonates were deprotected to access the corresponding -aminoarylphosphonic acids.

摘要

摘要

各种芳胺经两步反应转化为 -Boc- -芳基磷酰胺酯。LiTMP和LDA在-78至0 °C的温度下诱导定向金属化反应。随后，磷原子及其取代基从氮原子向α-碳负离子碳原子发生[1,3]迁移，生成 -Boc保护的 -氨基芳基膦酸酯。3-取代苯基磷酰胺酯的取代基性质对膦酸酯形成的区域选择性有很大影响。用氘代磷酰胺酯进行的交叉实验证明了重排反应的分子内过程。对三种代表性的 -Boc- -氨基芳基膦酸酯进行脱保护，得到相应的 -氨基芳基膦酸。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/35dd/5738464/08c6e38d813d/706_2017_2058_Sch8_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/35dd/5738464/239404250fd7/706_2017_2058_Sch1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/35dd/5738464/b16c6567cd4a/706_2017_2058_Sch2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/35dd/5738464/08dd078f84f1/706_2017_2058_Sch3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/35dd/5738464/85455ee1e373/706_2017_2058_Sch4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/35dd/5738464/e74502b9e22e/706_2017_2058_Sch5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/35dd/5738464/65efb735c6cd/706_2017_2058_Sch6_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/35dd/5738464/e2c8ecdd1c45/706_2017_2058_Sch7_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/35dd/5738464/08c6e38d813d/706_2017_2058_Sch8_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/35dd/5738464/239404250fd7/706_2017_2058_Sch1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/35dd/5738464/b16c6567cd4a/706_2017_2058_Sch2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/35dd/5738464/08dd078f84f1/706_2017_2058_Sch3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/35dd/5738464/85455ee1e373/706_2017_2058_Sch4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/35dd/5738464/e74502b9e22e/706_2017_2058_Sch5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/35dd/5738464/65efb735c6cd/706_2017_2058_Sch6_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/35dd/5738464/e2c8ecdd1c45/706_2017_2058_Sch7_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/35dd/5738464/08c6e38d813d/706_2017_2058_Sch8_HTML.jpg

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