Enantioselective Total Synthesis and Absolute Configuration Assignment of (+)-Toxicodenane A

被引:3
作者
Qin, Xu-Long [1 ,2 ]
Wu, Guo-Jie [1 ,3 ]
Han, Fu-She [1 ,2 ]
机构
[1] Chinese Acad Sci, Changchun Inst Appl Chem, Key Lab Synthet Rubber, Jilin 130022, Jilin, Peoples R China
[2] Univ Sci & Technol China, Hefei 230026, Anhui, Peoples R China
[3] Chinese Acad Sci, Shanghai Inst Organ Chem, Key Lab Synthet Chem Nat Subst, Shanghai 200032, Peoples R China
基金
中国国家自然科学基金;
关键词
MEDIUM-SIZED CARBOCYCLES; CONSTRUCTION; COMBINATION;
D O I
10.1021/acs.orglett.1c03293
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
We present the first enantioselective total synthesis and absolute configuration assignment of (+)-toxicodenane A via a nine-step sequence from the readily available material. The synthesis features a desymmetric enantioselective reduction of 2,2-disubstituted 1,3-cyclohexanedione for the synthesis of a chiral 2,2-disubstituted 3-hydroxy cyclohexanone building block, a highly diastereoselective Grignard reaction for the incorporation of an allyl group, and a Lewis acid-mediated intramolecular transacetalation and Prins cascade reaction for the construction of oxa-bridged bicyclic rings.
引用
收藏
页码:8570 / 8574
页数:5
相关论文
共 26 条
[1]   Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C=N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin-Anh and Chelation-Control Models [J].
Bartolo, Nicole D. ;
Read, Jacquelyne A. ;
Valentin, Elizabeth M. ;
Woerpel, K. A. .
CHEMICAL REVIEWS, 2020, 120 (03) :1513-1619
[2]   Identification of an unexpected 2-oxonia[3,3]sigmatropic rearrangement/aldol pathway in the formation of oxacyclic rings. Total synthesis of (+)-aspergillin PZ [J].
Canham, Stephen M. ;
Overman, Larry E. ;
Tanis, Paul S. .
TETRAHEDRON, 2011, 67 (51) :9837-9843
[3]   A Total Synthesis of (-)-Hamigeran B and (-)-4-Bromohamigeran B [J].
Cao, Bao-Chen ;
Wu, Guo-Jie ;
Yu, Fang ;
He, Yu-Peng ;
Han, Fu-She .
ORGANIC LETTERS, 2018, 20 (12) :3687-3690
[4]   Efforts toward the total synthesis of (±)-toxicodenane A utilizing an oxidopyrylium-based [5+2] cycloaddition of a silicon-tethered BOC-pyranone [J].
Grabowski, Jacob P. ;
Ferrence, Gregory M. ;
Mitchell, T. Andrew .
TETRAHEDRON LETTERS, 2020, 61 (38)
[5]   Two New Sesquiterpenes from the Resin of Toxicodendron vernicifluum [J].
He, Jiang-Bo ;
Lu, Qing ;
Cheng, Yong-Xian .
HELVETICA CHIMICA ACTA, 2015, 98 (07) :1004-1008
[6]   Sesquiterpenoids with New Carbon Skeletons from the Resin of Toxicodendron vernicifluum as New Types of Extracellular Matrix Inhibitors [J].
He, Jiang-Bo ;
Luo, Jie ;
Zhang, Li ;
Yan, Yong-Min ;
Cheng, Yong-Xian .
ORGANIC LETTERS, 2013, 15 (14) :3602-3605
[7]   SUBSTRATE-DIRECTABLE CHEMICAL-REACTIONS [J].
HOVEYDA, AH ;
EVANS, DA ;
FU, GC .
CHEMICAL REVIEWS, 1993, 93 (04) :1307-1370
[8]   Diastereoselective Total Synthesis of (±)-Toxicodenane A [J].
Kobayashi, Toyoharu ;
Yamanoue, Kotono ;
Abe, Hideki ;
Ito, Hisanaka .
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2017, 2017 (45) :6693-6699
[9]   Total Syntheses of Aflavazole and 14-Hydroxyaflavinine [J].
Li, Hailong ;
Chen, Qifeng ;
Lu, Zhaohong ;
Li, Ang .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (48) :15555-15558
[10]   Practical asymmetric approach to medium-sized carbocycles based on the combination of two Ru-catalyzed transformations and a lewis acid-induced cyclization [J].
López, F ;
Castedo, L ;
Mascareñas, JL .
ORGANIC LETTERS, 2005, 7 (02) :287-290