Towards the Total Synthesis of Mycaperoxide B: Probing Biosynthetic Rationale

被引:11
作者
Silva, Eduarda M. P. [2 ]
Pye, Richard J. [1 ]
Brown, Geoffrey D. [1 ]
Harwood, Laurence M. [1 ]
机构
[1] Univ Reading, Dept Chem, Reading RG6 6AD, Berks, England
[2] Univ Aveiro, Dept Chem, QOPNA, P-3810193 Aveiro, Portugal
关键词
Natural products; Biomimetic synthesis; Michael addition; Peroxides; Oxygen heterocycles; NORSESTERTERPENE CYCLIC PEROXIDES; AUSTRALIAN MARINE SPONGE; VITRO ANTIMALARIAL ACTIVITY; ASYMMETRIC EPOXIDATION; BIOMIMETIC APPROACH; CYCLOADDITION; 1,2-DIOXANES; ALKENES; ANALOGS;
D O I
10.1002/ejoc.201101477
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Studies towards the biomimetic synthesis of mycaperoxide B (1) are described. We have established the synthesis of four diastereoisomers of mycaperoxide B methyl ester (1a) by employing a Michael addition across an a,beta-unsaturated ester precursor 2 as the key step. This result strongly suggestsstereocontrol in the addition of the hydroperoxide functionality to the E double bond and discloses the importance of choosing the correct geometry of the a,beta-unsaturated double bond when attempting to synthesise mycaperoxide B. Four diastereoisomeric tetrahydrofurans derived from an intramolecular rearrangement of the 1,2-dioxolane enolate 12 were also isolated and characterised.
引用
收藏
页码:1209 / 1216
页数:8
相关论文
共 38 条
[1]  
ADOLFSSON H, 2004, MODERN OXIDATION MET, P21, DOI DOI 10.1002/3527603689.CH211421798
[2]   SYNTHESIS OF POLYETHER-TYPE TETRAHYDROFURANS VIA HYDROPEROXIDE CYCLIZATION [J].
BARTLETT, PA ;
CHAPUIS, C .
JOURNAL OF ORGANIC CHEMISTRY, 1986, 51 (14) :2799-2806
[3]  
Capon RJ, 2001, EUR J ORG CHEM, V2001, P633
[4]   2 NEW NORSESTERTERPENE CYCLIC PEROXIDES FROM A MARINE SPONGE, MYCALE (CARMIA) CF SPONGIOSA [J].
CAPON, RJ .
JOURNAL OF NATURAL PRODUCTS, 1991, 54 (01) :190-195
[5]   Cyclic peroxides and related norterpenes from a southern Australian marine sponge, Mycale sp. [J].
Capon, RJ ;
Rochfort, SJ ;
Ovenden, SPB .
JOURNAL OF NATURAL PRODUCTS, 1997, 60 (12) :1261-1264
[6]   TRUNCULIN-A AND TRUNCULIN-B, NORSESTERTERPENE CYCLIC PEROXIDES FROM A MARINE SPONGE, LATRUNCULIA-BREVIS [J].
CAPON, RJ ;
MACLEOD, JK ;
WILLIS, AC .
JOURNAL OF ORGANIC CHEMISTRY, 1987, 52 (03) :339-342
[7]   Mycaperoxides F and G and a related norterpene ketone from southern Australian marine sponges, Mycale species [J].
Capon, RJ ;
Rochfort, SJ ;
Ovenden, SPB ;
Metzger, RP .
JOURNAL OF NATURAL PRODUCTS, 1998, 61 (04) :525-528
[8]   STRUCTURAL AND STEREOCHEMICAL STUDIES ON MARINE NORTERPENE CYCLIC PEROXIDES [J].
CAPON, RJ ;
MACLEOD, JK .
TETRAHEDRON, 1985, 41 (16) :3391-3404
[9]   Asymmetric epoxidation of electron-deficient olefins [J].
Diez, David ;
Nunez, Marta G. ;
Anton, Ana B. ;
Garcia, P. ;
Moro, R. F. ;
Garrido, N. M. ;
Marcos, Isidro S. ;
Basabe, P. ;
Urones, Julio G. .
CURRENT ORGANIC SYNTHESIS, 2008, 5 (03) :186-216
[10]  
Drew MGB, 1999, SYNLETT, P185