Total Synthesis of Beshanzuenone D and Its Epimers and Abiespiroside A

被引：17

作者：

Borade, Balasaheb R. ^{[1
,2
]}

Dixit, Ruchi ^{[2
,3
]}

Kontham, Ravindar ^{[1
,2
]}

机构：

[1] CSIR, Organ Chem Div, Natl Chem Lab, Pune 411008, Maharashtra, India

[2] Acad Sci & Innovat Res AcSIR, Ghaziabad 201002, India

[3] CSIR, Phys & Mat Chem Div, Natl Chem Lab, Pune 411008, Maharashtra, India

来源：

ORGANIC LETTERS | 2020年 / 22卷 / 21期

关键词：

D O I：

10.1021/acs.orglett.0c03157

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A unified and protecting-group-free six-step total synthesis of bisabolane-type sesquiterpenoid beshanzuenone D and its stereoisomers and abiespiroside A using S-(+)-carvone as a common chiral-pool building block is disclosed. This synthetic route features chemoselective allylic chlorination of carvone, Au(I)-catalyzed cydoisomerization induced construction of furan from homopropargylic diol, substrate-controlled selective hydroxylation using Davis-oxaziridine, and dye-sensitized photo-oxidation (through O-1(2)) of hydroxyalkyl tethered furan to access oxaspirolactone as key transformations. A comprehensive set of NMR data along with DFT calculations, ECD spectra, and optical rotation measurements of the synthesized beshanzuenone D and its epimers were obtained to confirm absolute configurations.

引用

收藏

页码：8561 / 8565

页数：5

相关论文

共 27 条

[1] Nonanomerlc spiroketals in natural products: Structures, sources, and synthetic strategies [J].

Aho, JE ;

Pihko, PM ;

Rissa, TK .

CHEMICAL REVIEWS, 2005, 105 (12) :4406-4440

[2] An Extremely Facile Synthesis of Furans, Pyrroles, and Thiophenes by the Dehydrative Cyclization of Propargyl Alcohols [J].

Aponick, Aaron ;

Li, Chuan-Ying ;

Malinge, Jeremy ;

Marques, Emerson Finco .

ORGANIC LETTERS, 2009, 11 (20) :4624-4627

[3] Total Synthesis, Biological Evaluation, and Target Identification of Rare Abies Sesquiterpenoids [J].

Davis, Dexter C. ;

Hoch, Dominic G. ;

Wu, Li ;

Abegg, Daniel ;

Martin, Brandon S. ;

Zhang, Zhong-Yin ;

Adibekian, Alexander ;

Dai, Mingji .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2018, 140 (50) :17465-17473

[4] 2-ARYLSULPHONYL-3-PHENYLOXAZIRIDINES - NEW CLASS OF STABLE OXAZIRIDINE DERIVATIVES [J].

DAVIS, FA ;

NADIR, UK ;

KLUGER, EW .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1977, (01) :25-26

[5] Recent applications of N-sulfonyloxaziridines (Davis oxaziridines) in organic synthesis [J].

Davis, Franklin A. .

TETRAHEDRON, 2018, 74 (26) :3198-3214

[6] Monoterpene and sesquiterpene synthases and the origin of terpene skeletal diversity in plants [J].

Degenhardt, Joerg ;

Koellner, Tobias G. ;

Gershenzon, Jonathan .

PHYTOCHEMISTRY, 2009, 70 (15-16) :1621-1637

[7] Natural sesquiterpenoids [J].

Fraga, Braulio M. .

NATURAL PRODUCT REPORTS, 2006, 23 (06) :943-972

[8]

FUKUDA H, 1979, SYNTHESIS-STUTTGART, P368

[9] Rare Sesquiterpenoids from the Shed Trunk Barks of the Critically Endangered Plant Abies beshanzuensis and Their Bioactivities [J].

Hu, Chang-Ling ;

Xiong, Juan ;

Li, Ji-Yang ;

Gao, Li-Xin ;

Wang, Wen-Xuan ;

Cheng, Ke-Jun ;

Yang, Guo-Xun ;

Li, Jia ;

Hu, Jin-Feng .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2016, 2016 (10) :1832-1835

[10] Total Synthesis of the Potent cAMP Signaling Agonist (-)-Alotaketal [J].

Huang, Jinhua ;

Yang, Jessica R. ;

Zhang, Jin ;

Yang, Jiong .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (21) :8806-8809