Bioinspired Total Synthesis of Bolivianine: A Diels - Alder/Intramolecular Hetero-Diels-Alder Cascade Approach

被引：99
作者：
Yuan, Changchun [1 ]
Du, Biao [1 ]
Yang, Li [1 ]
Liu, Bo [1 ,2 ]
机构：
[1] Sichuan Univ, Coll Chem, Minist Educ, Key Lab Green Chem & Technol, Chengdu 610064, Sichuan, Peoples R China
[2] Shanghai Inst Organ Chem, Key Lab Synthet Chem Nat Subst, Shanghai 200032, Peoples R China
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2013年 / 135卷 / 25期
关键词：
ENANTIOSELECTIVE TOTAL-SYNTHESIS; CATALYZED 4+2 CYCLOADDITION; ASYMMETRIC TOTAL-SYNTHESIS; SESQUITERPENE LACTONE; BIOMIMETIC SYNTHESES; BUILDING-BLOCKS; BIOSYNTHESIS; CONCISE; (E)-BETA-OCIMENE; DERIVATIVES;
D O I：
10.1021/ja4040335
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
We report the first total synthesis of bolivanine in a 14 step pathway involving the synthesis of onoseriolide. Our synthesis features a palladium-catalyzed intramolecular cyclopropanation involving an allylic metal carbene and a Diels-Alder/intramolecular hetero-Diels-Alder cascade, allowing the single-step assembly of a tricyclic system with proper configuration. The synthetic efforts validate our modified biogenetic hypothesis and allow us to confirm the absolute configuration of bolivianine.
引用
收藏
页码：9291 / 9294
页数：4
相关论文
共 54 条
[1]   Bolivianine, a new sesterpene with an unusual skeleton from Hedyosmum angustifolium, and its isomer, isobolivianine [J].
Acebey, Lucia ;
Sauvain, Michel ;
Beck, Stephan ;
Moulis, Claude ;
Gimenez, Aberto ;
Jullian, Valerie .
ORGANIC LETTERS, 2007, 9 (23) :4693-4696
[2]   Anti-Leishmanial Lindenane Sesquiterpenes from Hedyosmum angustifolium [J].
Acebey, Lucia ;
Jullian, Valerie ;
Sereno, Denis ;
Chevalley, Severine ;
Estevez, Yannick ;
Moulis, Claude ;
Beck, Stephan ;
Valentin, Alex ;
Gimenez, Alberto ;
Sauvain, Michel .
PLANTA MEDICA, 2010, 76 (04) :365-U61
[3]   5-METHYLENE-2(5H)-FURANONE AS A DIENOPHILE IN DIELS-ALDER CYCLOADDITIONS - SITE SELECTIVITY AND REGIOSELECTIVITY [J].
ALONSO, D ;
ORTI, J ;
BRANCHADELL, V ;
OLIVA, A ;
ORTUNO, RM ;
BERTRAN, J ;
FONT, J .
JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (10) :3060-3063
[4]   Intermolecular Metal-Free Cyclopropanation of Alkenes Using Tosylhydrazones [J].
Barluenga, Jose ;
Quinones, Noelia ;
Tomas-Gamasa, Maria ;
Cabal, Maria-Paz .
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2012, 2012 (12) :2312-2317
[5]   NATURALLY-OCCURRING TERPENE DERIVATIVES .254. ONOSERIOLIDE, NEW SESQUITERPENE LACTONE FROM ONOSERIS-ALBICANS [J].
BOHLMANN, F ;
ZDERO, C ;
KING, RM ;
ROBINSON, H .
PHYTOCHEMISTRY, 1980, 19 (04) :689-691
[6]   5-YLIDENE-2(5H)-FURANONES AS DIENOPHILES IN DIELS-ALDER CYCLOADDITIONS - EFFECT OF THE SUBSTITUENTS ON THE SITE-SELECTIVITY [J].
BRANCHADELL, V ;
FONT, J ;
OLIVA, A ;
ORTI, J ;
ORTUNO, RM ;
RAFEL, S ;
TERRIS, N ;
VENTURA, M .
TETRAHEDRON, 1991, 47 (41) :8775-8786
[7]   Silver Nanoparticle-Catalyzed Diels-Alder Cycloadditions of 2′-Hydroxychalcones [J].
Cong, Huan ;
Becker, Clinton F. ;
Elliott, Sean J. ;
Grinstaff, Mark W. ;
Porco, John A., Jr. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (21) :7514-7518
[8]   Formal synthesis of Abyssomicin C [J].
Couladouros, Elias A. ;
Bouzas, Emmanuel A. ;
Magos, Alexandros D. .
TETRAHEDRON, 2006, 62 (22) :5272-5279
[9]  
DEMEIJERE A, 1991, SYNTHESIS-STUTTGART, P547
[10]   Total Synthesis of (-)-Fusarisetin A and Reassignment of the Absolute Configuration of Its Natural Counterpart [J].
Deng, Jun ;
Zhu, Bo ;
Lu, Zhaoyong ;
Yu, Haixin ;
Li, Ang .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (02) :920-923
123456