(+)-Saxitoxin, a potent neurotoxin and NaV blocker, poses significant synthetic challenges due to its compact tricyclic framework and guanidinium moieties. We report a concise and asymmetric total synthesis featuring an intramolecular [2 + 2] photocycloaddition of an alkenylboronate ester equipped with a new chiral auxiliary. This auxiliary, compatible with UV light and easily exchangeable on B(pin) derivatives, enabled high stereocontrol through hydrogen-bond-mediated transition-state stabilization. Our approach not only introduces an innovative surrogate for intramolecular Michael addition, particularly addressing transformations with contra-thermodynamic barriers, but also highlights the potential of boron-enabled photochemistry for synthesizing complex molecules.
Journal of the American Chemical Society. 2025 Mar 10. doi: 10.1021/jacs.5c00666 Q115.62025
Synthesis of (+)-Saxitoxin Facilitated by a Chiral Auxiliary for Photocycloadditions Involving Alkenylboronate Esters
手性辅助剂促进的烯基硼酸酯光环加成在合成(+)-石房哈毒素中的应用研究 翻译改进
作者单位 +展开
作者单位
DOI: 10.1021/jacs.5c00666 PMID: 40062953
摘要 Ai翻译
相关内容
-
(S,S)-(+)-pseudoephedrine as chiral auxiliary in asymmetric aza-Michael reactions. Unexpected selectivity change when manipulating the structure of the auxiliary
手性辅助剂(S,S)-(＋)-伪麻黄碱在不对称aza-迈克尔加成反应中的应用及其结构对映选择性的改变
The Journal of organic chemistry. 2005 Oct 28;70(22):8790-800.
-
Diastereoselective Diels-Alder reactions of a novel cyclopropenyl-containing chiral auxiliary
含有环丙烯基的手性辅助剂的差向选择性狄尔斯-阿尔德反应
Organic letters. 2007 Dec 6;9(25):5167-70.
-
Highly efficient asymmetric vinylogous Mannich reaction induced by O-pivaloylated D-galactosylamine as the chiral auxiliary
由O-特丁酰基-D-半乳糖胺诱导的高效不对称烯氨基曼尼希反应（ vinylethynyl 替换为 “vinylogous”）
Organic & biomolecular chemistry. 2011 Mar 21;9(6):1756-62.
-
Highly Enantioselective Aldol Reaction: Development of a New Chiral Auxiliary from cis-1-Amino-2-hydroxyindan
高对映选择性 aldol 反应：由顺式 1-氨基-2-羟基茚发展而来的新型手性辅助剂
Journal of the Chemical Society. Chemical communications. 1992;1992(22):1673-1674.
-
Enantioselective Electrophilic Aromatic Nitration: A Chiral Auxiliary Approach
对映选择性亲电芳香族硝化：手性辅助剂法
Angewandte Chemie (International ed. in English). 2019 Jan 21;58(4):1035-1040.
-
Enantiocomplementary enzymatic resolution of the chiral auxiliary: cis,cis-6-(2,2-dimethylpropanamido)spiro[4.4]nonan-1-ol and the molecular basis for the high enantioselectivity of subtilisin Carlsberg
卡尔斯伯克蛋白酶对映选择性催化解析辅助剂：顺，顺-6-(2,2-二甲基丙酰氨基)螺[4.4]壬烷-1-醇及高的对映选择性的分子基础
Chembiochem : a European journal of chemical biology. 2004 Jul 5;5(7):980-7.
-
Photoremovable chiral auxiliary
光解型手性辅助剂
Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology. 2012 Mar;11(3):500-7.
-
General and stereoselective aminoxylation of biradical titanium(iv) enolates with TEMPO: a detailed study on the effect of the chiral auxiliary
手性辅助剂对TEMPO介导的钛(IV)叶立德亚胺氧𬭩化反应的影响研究
Organic & biomolecular chemistry. 2018 Jul 4;16(26):4807-4815.
