（-）-瓦莱辛的对映选择性合成：通过复杂吲哚硼化实现晚期 C17-氧化。
Enantioselective Synthesis of (-)-Vallesine: Late-Stage C17-Oxidation via Complex Indole Boronation.
机构信息
Department of Chemistry , Massachusetts Institute of Technology , Cambridge , Massachusetts 02139 , United States.
出版信息
Org Lett. 2018 Jun 15;20(12):3647-3650. doi: 10.1021/acs.orglett.8b01428. Epub 2018 Jun 4.
Abstract
The first enantioselective total synthesis of (-)-vallesine via a strategy that features a late-stage regioselective C17-oxidation followed by a highly stereoselective transannular cyclization is reported. The versatility of this approach is highlighted by the divergent synthesis of the archetypal alkaloid of this family, (+)-aspidospermidine, and an A-ring-oxygenated derivative, (+)-deacetylaspidospermine, the precursor to (-)-vallesine, from a common intermediate.
摘要
本文报道了通过一种策略实现（-）-瓦莱辛的首次对映选择性全合成，该策略的特点是晚期 C17-选择性氧化，然后是高度对映选择性的环加成。这种方法的多功能性通过该家族原型生物碱（+）-表阿朴长春碱和 A 环氧化衍生物（+）-去乙酰表阿朴长春胺的发散合成得到了突出体现，它们是（-）-瓦莱辛的前体，均由一个共同的中间体制备得到。
相似文献
1
Enantioselective Synthesis of (-)-Vallesine: Late-Stage C17-Oxidation via Complex Indole Boronation.（-）-瓦莱辛的对映选择性合成：通过复杂吲哚硼化实现晚期 C17-氧化。
Org Lett. 2018 Jun 15;20(12):3647-3650. doi: 10.1021/acs.orglett.8b01428. Epub 2018 Jun 4.
2
Total Synthesis of (-)-Alstofolinine A through a Furan Oxidation/Rearrangement and Indole Nucleophilic Cyclization Cascade.通过呋喃氧化/重排和吲哚亲核环化级联反应全合成（-）-阿洛司福林 A
Angew Chem Int Ed Engl. 2019 Apr 1;58(15):4988-4991. doi: 10.1002/anie.201900156. Epub 2019 Mar 6.
3
Enantioselective Total Synthesis of Cymoside through a Bioinspired Oxidative Cyclization of a Strictosidine Derivative.通过严格斯梯烷衍生物的生物灵感氧化环化反应对卫矛苷进行对映选择性全合成。
Angew Chem Int Ed Engl. 2020 Jan 20;59(4):1527-1531. doi: 10.1002/anie.201912812. Epub 2019 Dec 4.
4
Concise and enantioselective total synthesis of (-)-mehranine, (-)-methylenebismehranine, and related Aspidosperma alkaloids.（-）-美拉宁、（-）-亚甲基双美拉宁及相关阿西多斯佩尔马生物碱的简洁对映选择性全合成。
Angew Chem Int Ed Engl. 2014 Oct 20;53(43):11634-9. doi: 10.1002/anie.201405609. Epub 2014 Sep 4.
5
Concise synthesis of the bicyclic scaffold of N-methylwelwitindolinone C isothiocyanate via an indolyne cyclization.通过吲哚炔环化反应简洁合成N-甲基维耳维丁吲哚酮C异硫氰酸酯的双环骨架。
Org Lett. 2009 Jun 4;11(11):2349-51. doi: 10.1021/ol9007684.
6
A short total synthesis of (+/-)-aspidospermidine.（±）-阿朴菲啶的简短全合成。
Org Lett. 2006 Mar 2;8(5):831-4. doi: 10.1021/ol052749q.
7
Protecting-Group-Free Formal Synthesis of Aspidospermidine: Ring-Opening Cyclization of Spirocyclopropane with Amine Followed by Regioselective Alkylations.无保护基策略的阿朴斯底碱全合成：螺环丙烷开环与胺的环化反应，随后进行区域选择性烷基化。
J Org Chem. 2019 Dec 20;84(24):15990-15996. doi: 10.1021/acs.joc.9b02469. Epub 2019 Dec 3.
8
Stereoselective synthesis of 3-alkylideneoxindoles by palladium-catalyzed cyclization reaction of 2-(alkynyl)aryl isocyanates with organoboron reagents.通过钯催化2-（炔基）芳基异氰酸酯与有机硼试剂的环化反应立体选择性合成3-亚烷基氧化吲哚。
Org Lett. 2008 Nov 6;10(21):4887-9. doi: 10.1021/ol801844w. Epub 2008 Oct 7.
9
Total Synthesis of (±)-Baphicacanthcusine A Enabled by Sequential Ring Contractions.（±）-Baphicacanthusinin A 的全合成：通过连续的环收缩实现。
Angew Chem Int Ed Engl. 2024 Oct 7;63(41):e202409139. doi: 10.1002/anie.202409139. Epub 2024 Sep 5.
10
Concise Total Syntheses of (+)-Haplocidine and (+)-Haplocine via Late-Stage Oxidation of (+)-Fendleridine Derivatives.通过 (+)-芬德利丁衍生物的晚期氧化，简洁地全合成 (+)-哈洛辛和 (+)-哈洛辛。
J Am Chem Soc. 2016 Sep 7;138(35):11383-9. doi: 10.1021/jacs.6b07623. Epub 2016 Aug 26.
引用本文的文献
1
Cyclic Imines and Their Salts as Universal Precursors in the Synthesis of Nitrogen-Containing Alkaloids.环状亚胺及其盐类作为含氮生物碱合成中的通用前体。
Int J Mol Sci. 2024 Dec 31;26(1):288. doi: 10.3390/ijms26010288.
2
Total Synthesis of Strempeliopidine and Non-Natural Stereoisomers through a Convergent Petasis Borono-Mannich Reaction.通过会聚 Petasis 硼诺-曼尼希反应的全合成 Strempeliopidine 和非天然对映异构体。
J Am Chem Soc. 2023 Apr 5;145(13):7278-7287. doi: 10.1021/jacs.2c13146. Epub 2023 Mar 23.
3
Total Synthesis of (-)-Kopsifoline A and (+)-Kopsifoline E.(-)-Kopsifoline A 和 (+)-Kopsifoline E 的全合成。
Org Lett. 2021 Dec 3;23(23):9118-9122. doi: 10.1021/acs.orglett.1c03448. Epub 2021 Nov 12.
4
Total Syntheses of Dihydroindole Alkaloids: Reductive Interrupted Fischer Indolization Followed by Redox Diversification.二氢吲哚生物碱的全合成：还原中断的费歇尔吲哚化反应，随后进行氧化还原多样化。
Org Lett. 2020 Jun 19;22(12):4675-4679. doi: 10.1021/acs.orglett.0c01472. Epub 2020 Jun 4.
本文引用的文献
1
Enantioselective Total Synthesis of (-)-Deoxoapodine.对映选择性全合成（-）-去氧阿朴啡碱。
Angew Chem Int Ed Engl. 2017 Oct 23;56(44):13857-13860. doi: 10.1002/anie.201708088. Epub 2017 Sep 27.
2
Divergent Asymmetric Total Synthesis of (+)-Vincadifformine, (-)-Quebrachamine, (+)-Aspidospermidine, (-)-Aspidospermine, (-)-Pyrifolidine, and Related Natural Products.(+)-Vincadifformine、(-)-Quebrachamine、(+)-Aspidospermidine、(-)-Aspidospermine、(-)-Pyrifolidine 及相关天然产物的发散不对称全合成
Org Lett. 2017 Jun 16;19(12):3167-3170. doi: 10.1021/acs.orglett.7b01292. Epub 2017 Jun 1.
3
Concise Total Syntheses of (+)-Haplocidine and (+)-Haplocine via Late-Stage Oxidation of (+)-Fendleridine Derivatives.通过 (+)-芬德利丁衍生物的晚期氧化，简洁地全合成 (+)-哈洛辛和 (+)-哈洛辛。
J Am Chem Soc. 2016 Sep 7;138(35):11383-9. doi: 10.1021/jacs.6b07623. Epub 2016 Aug 26.
4
Direct C7 Functionalization of Tryptophan. Synthesis of Methyl ()-2-((-Butoxycarbonyl)amino)-3-(7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-indol-3-yl)propanoate.色氨酸的直接C7官能化。() - 2 - （（叔丁氧羰基）氨基）- 3 - （7 - （4,4,5,5 - 四甲基 - 1,3,2 - 二氧杂硼烷 - 2 - 基）- 1 - 吲哚 - 3 - 基）丙酸甲酯的合成。
Organic Synth. 2015;92:373-385. doi: 10.15227/orgsyn.092.0373.
5
Total Synthesis of Verruculogen and Fumitremorgin A Enabled by Ligand-Controlled C-H Borylation.配体控制的C-H硼化实现疣孢菌素和烟曲霉震颤素A的全合成
J Am Chem Soc. 2015 Aug 19;137(32):10160-3. doi: 10.1021/jacs.5b07154. Epub 2015 Aug 11.
6
Direct Observation of Intermediates Involved in the Interruption of the Bischler-Napieralski Reaction.对参与比施勒-纳皮耶拉尔斯基反应中断过程的中间体的直接观察
J Org Chem. 2015 Aug 7;80(15):7403-11. doi: 10.1021/acs.joc.5b01023. Epub 2015 Jul 22.
7
A procedure for transforming indoles into indolequinones.一种将吲哚转化为吲哚醌的方法。
J Org Chem. 2015 Jan 16;80(2):1006-17. doi: 10.1021/jo502509s. Epub 2015 Jan 6.
8
C7-derivatization of C3-alkylindoles including tryptophans and tryptamines.包括色氨酸和色胺在内的C3-烷基吲哚的C7衍生化。
J Org Chem. 2014 Nov 21;79(22):11254-63. doi: 10.1021/jo502062z. Epub 2014 Nov 10.
9
Unified strategy to monoterpene indole alkaloids: total syntheses of (±)-goniomitine, (±)-1,2-dehydroaspidospermidine, (±)-aspidospermidine, (±)-vincadifformine, and (±)-kopsihainanine A.单萜吲哚生物碱的统一策略：（±）-钩吻碱、（±）-1,2-脱氢阿朴斯碱、（±）-阿朴斯碱、（±）-长春多卡辛和（±）-考斯海南宁 A 的全合成。
J Am Chem Soc. 2014 Oct 22;136(42):15102-8. doi: 10.1021/ja509329x. Epub 2014 Oct 13.
10
Concise and enantioselective total synthesis of (-)-mehranine, (-)-methylenebismehranine, and related Aspidosperma alkaloids.（-）-美拉宁、（-）-亚甲基双美拉宁及相关阿西多斯佩尔马生物碱的简洁对映选择性全合成。
Angew Chem Int Ed Engl. 2014 Oct 20;53(43):11634-9. doi: 10.1002/anie.201405609. Epub 2014 Sep 4.
Zotero 插件