A unified strategy for enantioselective total synthesis of cladiellin and briarellin diterpenes: Total synthesis of briarellins E and F and the putative structure of alcyonin and revision of its structure assignment

Journal of Organic Chemistry

Volumn 74, Issue 15, 2009, Pages 5458-5470

  Corminboeuf, Olivier ^a,b   Overman, Larry E ^a   Pennington, Lewis D ^a,c  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b ACTELION PHARMACEUTICALS LTD   (Switzerland)

^c AMGEN INC   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL EQUATIONS; CHEMICAL TRANSFORMATIONS; DITERPENE; DITERPENES; ENANTIOSELECTIVE TOTAL SYNTHESIS; SPECTRAL DATA; STEREOCENTERS; TOTAL SYNTHESIS; UNIFIED APPROACH; UNSATURATED ALDEHYDES;

ALDEHYDES; OLEFINS;

SYNTHESIS (CHEMICAL);

11 ACETOXY 4 DEOXYASBESTININ D; 3 ACETOXY 4 HYDROXY 4 4,5 EPOXY 4 METHYL 7 [1 METHYL 2 (TRIISOPROPYLSILYLOXY)ETHYL] 3 PROP 2 YNYL 1,3,3A,6,7, 7A HEXAHYDROISOBENZOFURAN 1 YL]PENTYL ESTER; 4 [4 METHYL 7 (1 METHYL 2 (TRIISOPROPYLSILYLOXY)ETHYL) 3 PROP 2 YNYL 1,3,3A,6,7,7A HEXAHYDROISOBENZOFURAN 1YL] PENT 3 EN 1 OL; 9,12 DIHYDROXY 6 ISOPROPYL 3,9 DIMETHYL 13 METHYLENE 15 OXATRICYCLO [6.6.1.0 0,0]PENTADEC 3 EN 10 YL ESTER; ACETIC ACID 3 ACETOXY 1 [3,4 DIHYDROXY 3,6,9 TRIMETHYL 2 PROP 2 YNYL 2A,5,5A,6,7,9,9A,9B OCTAHYDRO 2H 1,8 DIOXABENZO(CD)AZULEN 9 YL]PROPYL ESTER; ACETIC ACID 3 ACETOXY 4 HYDROXY 4 [4, 5 EPOXY 4 METHYL 7 (1 METHYL 2 (TRIISOPROPYLSILYLOXY)ETHYL) 3 PROP 2 YNYL 1,3,3A,6,7,7A HEXAHYDROISOBENZOFURAN 1 YL]PENTYL ESTER; ALCYONIN; ALDEHYDE DERIVATIVE; ALLYLIC PEROXIDE; ALPHA,BETA UNSATURATED ALDEHYDE DERIVATIVE; ASBESTININ 12; ASBESTININ DITERPENE DERIVATIVE; BRIARELLIN DITERPENE; BRIARELLIN E; BRIARELLIN F; CLADIELLAPEROXIDE; CLADIELLIN DITERPENE ALCYONIN; CYCLOHEXADIENYL DIOL DERIVATIVE; DIHYDROXY 4 (7 ISOPROPYL 4 METHYL 3 PROP 2 YNYL 1,3,3A,6,7,7A HEXAHYDROISOBENZOFURAN 1 YL)PENTYL ALCOHOL; DITERPENE; ESTER DERIVATIVE; FURAN DERIVATIVE; HEXAHYDROISOBENZOFURAN; OXACYCLONONANE; PEROXIDE; TRICYCLIC HYDROXY DIESTER; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; CONTROLLED STUDY; DEOXYGENATION; ENANTIOSELECTIVITY; METABOLITE; OXYGENATION; REACTION ANALYSIS; SPECTROSCOPY; STEREOCHEMISTRY; STRUCTURE ANALYSIS; SYNTHESIS;

DITERPENES; ETHERS, CYCLIC; MOLECULAR CONFORMATION; STEREOISOMERISM; STEROIDS;

EID: 68049113576     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9010156     Document Type: Article

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160. We thank Prof. A. Rodríguez of the University of Puerto Rico, Río Piedras, for providing a sample of natural briarellin E.
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165. We thank Prof. A. Rodríguez of the University of Puerto Rico, Río Piedras, for providing a sample of natural 11-acetoxy-4- deoxyasbestinin D.
166. The limited amount of diene 61 available (∼8 mg) precluded an extensive investigation of RCM conditions.
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169. 89 had preceded ring closure.
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171. 16e,16f
172. The structure for this compound (S4) can be found in the Supporting Information.