在 vinylogous Payne 重排过程中的动力学拆分：（+）-海鞘素极性药效团亚单位的简洁合成。
Dynamic kinetic resolution during a vinylogous Payne rearrangement: a concise synthesis of the polar pharmacophoric subunit of (+)-scyphostatin.
机构信息
Department of Chemistry, 207 Pleasant Street, SE, University of Minnesota, Minneapolis, Minnesota 55455, USA.
出版信息
Org Lett. 2010 Jan 1;12(1):52-5. doi: 10.1021/ol902459z.
Abstract
The diastereomeric epoxycyclohexenols 3a/b (obtained via a Wharton rearrangement of a bis-epoxycyclohexanone precursor) were shown to undergo interconversion via a facile vinylogous Payne rearrangement. Mechanistic issues were probed; the doubly O-deuterated analogues underwent this equilibration more slowly than the parent dihydroxy compounds. It was possible to kinetically resolve the mixture of 3a/b under equilibrating conditions by use of Amano PS. This DKR is additionally noteworthy because it sets four stereocenters in a single event.
摘要
（通过双环氧环己烷酮前体的 Wharton 重排得到的）非对映环氧环己烯醇 3a/b 可以通过容易的 vinylogous Payne 重排进行互变。机理问题进行了探讨；双 O-氘代类似物的这种平衡比母体二羟基化合物更慢。在平衡条件下，使用 Amano PS 可以动力学拆分 3a/b 的混合物。这种 DKR 值得注意，因为它在单个事件中设置了四个立体中心。
相似文献
1
Dynamic kinetic resolution during a vinylogous Payne rearrangement: a concise synthesis of the polar pharmacophoric subunit of (+)-scyphostatin.在 vinylogous Payne 重排过程中的动力学拆分：（+）-海鞘素极性药效团亚单位的简洁合成。
Org Lett. 2010 Jan 1;12(1):52-5. doi: 10.1021/ol902459z.
2
Synthesis and evaluation of three novel scyphostatin analogues as neutral sphingomyelinase inhibitors.三种新型水母鞘抑素类似物作为中性鞘磷脂酶抑制剂的合成与评价
Chembiochem. 2003 Nov 7;4(11):1223-5. doi: 10.1002/cbic.200300667.
3
Short and efficient route to the fully functionalized polar core of scyphostatin.通往水母毒素完全功能化极性核心的简短而高效的途径。
Org Lett. 2005 May 26;7(11):2245-8. doi: 10.1021/ol0506359.
4
Concise asymmetric total synthesis of scyphostatin, a potent inhibitor of neutral sphingomyelinase.鞘磷脂酶强效抑制剂缢虫素的简洁不对称全合成
Chemistry. 2007;13(36):10225-38. doi: 10.1002/chem.200700871.
5
Studies toward the total synthesis of scyphostatin: first entry to the highly functionalized cyclohexenone segment.关于水母毒素全合成的研究：首次进入高度官能化的环己烯酮片段。
Org Lett. 2001 May 31;3(11):1653-6. doi: 10.1021/ol015873s.
6
Concise approach to the carbocyclic core of the naturally occurring sphingomyelinase inhibitor scyphostatin.简洁构建天然鞘氨醇磷酸酯酶抑制剂海兔毒素的碳环核心。
J Org Chem. 2013 Apr 5;78(7):3367-73. doi: 10.1021/jo3028196. Epub 2013 Mar 6.
7
Synthesis of Scyphostatin Analogues through Hypervalent Iodine-Mediated Phenol Dearomatization.通过高价碘介导的酚类脱芳构化合成海鞘素类似物。
J Org Chem. 2017 Nov 17;82(22):11816-11828. doi: 10.1021/acs.joc.7b02366. Epub 2017 Oct 18.
8
A furan Diels-Alder cycloaddition approach to scyphostatin analogues.呋喃 Diels-Alder 环加成方法合成海鞘素类似物。
Org Biomol Chem. 2012 Dec 7;10(45):9058-66. doi: 10.1039/c2ob26793d. Epub 2012 Oct 19.
9
Total synthesis of (+)-scyphostatin, a potent and specific inhibitor of neutral sphingomyelinase.强效特异性中性鞘磷脂酶抑制剂（+）-水母鞘素的全合成
Angew Chem Int Ed Engl. 2004 Aug 13;43(32):4207-9. doi: 10.1002/anie.200454192.
10
A strategy for the late-stage divergent syntheses of scyphostatin analogues.一种海鞘素类似物晚期发散合成的策略。
J Org Chem. 2011 Mar 4;76(5):1361-71. doi: 10.1021/jo102327e. Epub 2011 Jan 21.
引用本文的文献
1
A copper-catalyzed asymmetric oxime propargylation enables the synthesis of the gliovirin tetrahydro-1,2-oxazine core.铜催化的不对称肟炔丙基化反应可实现胶质病毒素四氢-1,2-恶嗪核心结构的合成。
Chem Sci. 2020 Oct 15;11(43):11897-11901. doi: 10.1039/d0sc04802j.
2
A strategy for the late-stage divergent syntheses of scyphostatin analogues.一种海鞘素类似物晚期发散合成的策略。
J Org Chem. 2011 Mar 4;76(5):1361-71. doi: 10.1021/jo102327e. Epub 2011 Jan 21.
本文引用的文献
1
Inhibition of sphingomyelin hydrolysis: targeting the lipid mediator ceramide as a key regulator of cellular fate.抑制鞘磷脂水解：以脂质介质神经酰胺作为细胞命运的关键调节因子为靶点。
Curr Med Chem. 2009;16(16):1978-2000. doi: 10.2174/092986709788682182.
2
Mosher ester analysis for the determination of absolute configuration of stereogenic (chiral) carbinol carbons.用于测定手性甲醇碳绝对构型的莫舍尔酯分析。
Nat Protoc. 2007;2(10):2451-8. doi: 10.1038/nprot.2007.354.
3
Concise asymmetric total synthesis of scyphostatin, a potent inhibitor of neutral sphingomyelinase.鞘磷脂酶强效抑制剂缢虫素的简洁不对称全合成
Chemistry. 2007;13(36):10225-38. doi: 10.1002/chem.200700871.
4
Stereoselective total synthesis of (+)-Scyphostatin via a pi-facially selective Diels-Alder reaction.通过π-面选择性狄尔斯-阿尔德反应实现（+）-水母毒素的立体选择性全合成。
J Org Chem. 2007 May 25;72(11):4117-25. doi: 10.1021/jo070337k. Epub 2007 May 4.
5
Influence of the scyphostatin side chain on the mode of inhibition of neutral sphingomyelinase.鞘氨醇抑制素侧链对中性鞘磷脂酶抑制模式的影响。
ChemMedChem. 2006 Jul;1(7):718-21. doi: 10.1002/cmdc.200600099.
6
Semisynthesis of C-ring modified triptolide analogues and their cytotoxic activities.C环修饰雷公藤甲素类似物的半合成及其细胞毒性活性。
Bioorg Med Chem Lett. 2006 Apr 1;16(7):1947-9. doi: 10.1016/j.bmcl.2005.12.098. Epub 2006 Feb 7.
7
Total synthesis of (+)-scyphostatin, a potent and specific inhibitor of neutral sphingomyelinase.强效特异性中性鞘磷脂酶抑制剂（+）-水母鞘素的全合成
Angew Chem Int Ed Engl. 2004 Aug 13;43(32):4207-9. doi: 10.1002/anie.200454192.
8
A nucleophile-catalyzed cycloisomerization permits a concise synthesis of (+)-harziphilone.亲核试剂催化的环异构化反应实现了(+)-哈齐菲隆的简洁合成。
Proc Natl Acad Sci U S A. 2004 Aug 17;101(33):12064-6. doi: 10.1073/pnas.0402563101. Epub 2004 Jul 1.
9
Studies directed toward the total synthesis of lactonamycin: control of the sense of cycloaddition of a quinone through directed intramolecular catalysis.针对内酯霉素全合成的研究：通过定向分子内催化控制醌的环加成方向。
Angew Chem Int Ed Engl. 2003 Nov 24;42(45):5625-9. doi: 10.1002/anie.200352591.
10
Chiral-Mn(salen)-complex-catalyzed kinetic resolution of secondary alcohols in water.手性锰（salen）配合物催化水中仲醇的动力学拆分
Angew Chem Int Ed Engl. 2003 Mar 3;42(9):1042-4. doi: 10.1002/anie.200390268.
Zotero 插件