從手性N-亞磺醯胺進行非對映選擇性磷酯基化反應建構高度選擇性的α-胺基磷酸酯;Synthesis of α-amino phosphonate from chiral N-sulfinyl imine via highly diastereoselective hydrophosphonylation

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题名:	從手性N-亞磺醯胺進行非對映選擇性磷酯基化反應建構高度選擇性的α-胺基磷酸酯;Synthesis of α-amino phosphonate from chiral N-sulfinyl imine via highly diastereoselective hydrophosphonylation
作者:	張聿辰;Chang, Yu-Chen
贡献者:	化學學系
关键词:	α-胺基磷酸酯;磷酯基化反應;普多維克反應;手性助劑;α-amino phosphonate;hydrophosphonylation;Pudovik-type reaction;chiral auxiliary
日期:	2023-08-21
上传时间:	2024-09-19 14:50:05 (UTC+8)
出版者:	國立中央大學
摘要:	普多維克反應是一種製備α-胺基磷酸酯的非鏡像選擇性磷酯基化反應，藉由該反應，我們希望能夠開發得到單一立體選擇性的α-胺基磷酸酯的合成方法。一般在進行普多維克反應需使用手性配位基來控制反應的立體選擇性，然而我們則是在手性胺基醛引入具備手性助劑特性的叔丁基亞磺醯胺，來有效控制反應的進行與否。研究結果說明，在左旋胺基醛引入具備手性助劑特性的官能基(R)-(+)-叔丁基亞磺醯胺，可有效進行反應，得到高立體選擇性產物。若是將左旋胺基醛起始物換成右旋胺基醛，則須引入(S)-(-)-叔丁基亞磺醯胺，方可以進行反應。這樣的化學反應就像模擬酵素生合成，具有立體選擇性及基質專一性。此外，該反應也不須在嚴苛條件下進行，只需要利用碳酸銫來促進反應，以溫和的條件下與各種天然與非天然胺基酸進行反應生成良好到優異產率的α-胺基磷酸酯。該方法同時展示反應基質的可用性、簡易實驗操作和原子經濟性等優點。;Pudovik reaction is a well-known diastereoselective C-P bond formation method for the synthesis of α-amino phosphonates. Despite the success of these reactions, there are still some limitations that must be addressed. Therefore, we would like to develop a user-friendly approach for the synthesis of α-amino phosphonates with high stereoselectivity. In general, chiral ligands are used to control the stereoselective Pudovik-type reactions. In this thesis, we demonstrated a Cs2CO3-mediated hydrophosphonylation for diastereoselective synthesis of α-amino phosphonates from the chiral sulfinimide. We used chiral 2-methyl-2-propanesulfinamide as a chiral auxiliary to prepare chiral sulfinimide from chiral α-amino aldehydes. This approach can achieve highly pronounced dichotomous selectivities for substrates, providing the diastereoisomers of the products in high yields. In addition, not only (S)-amino aldehydes can be suitable for the reaction by using (R)-(+)-2-methyl-2-propanesulfinamide, but (R)-amino aldehydes can also be reacted by using (S)-(-)-2-methyl-2-propanesulfinamide. Furthermore, this diastereoselective hydrophosphonylation is simple protocol using Cs2CO3-mediated reactions under mild reaction conditions from various natural and unnatural amino acids can be reacted to generate relative α-amino phosphonates. The method also shows the advantages of substrate scopes, user-friendly experimental operation and atom economy.
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