Diels-Alder reactions of heterocyclic azadienes: total synthesis of PDE-II methyl ester

1986 ◽  
Vol 51 (16) ◽  
pp. 3250-3252 ◽  
Author(s):  
Dale L. Boger ◽  
Robert S. Coleman
Keyword(s):  
Methyl Ester ◽  
Total Synthesis ◽  
Diels Alder

scholarly journals Stereoselective total syntheses of (±)-sinularene and (±)-5-epi-sinularene: a general intramolecular Diels–Alder approach to tricyclic sesquiterpenes

1985 ◽  
Vol 63 (4) ◽  
pp. 993-995 ◽  
Author(s):  
Kazimierz Antczak ◽  
John F. Kingston ◽  
Alex G. Fallis
Keyword(s):  
Double Bond ◽  
Methyl Ester ◽  
Total Synthesis ◽  
Ring System ◽  
Diels Alder ◽  
Exocyclic Double Bond ◽  
Total Syntheses ◽  
Methyl Group ◽  
Secondary Hydroxyl ◽  
Selective Hydrogenolysis

Stereoselective total synthesis of (±)-sinularene and (±)-5-epi-sinularene are described. The sequence employs a "blocked" cyclopentadiene in which the cyclopropane unit also serves as a latent methyl group. Thus intramolecular [4 + 2] cycloaddition of the substituted methyl spiro[2.4]hepta-4,6-dien-1-yl)-2-pentenoate 11 affords 5-benzyloxy-6-isopropyl-8-carbomethoxytetracyclo[5.4.01,7.02,4.02,9]undec-10-ene (12) which after selective hydrogenolysis generates the tricyclo[4.4.01,6.02,8]decane (sinularene) ring system. Removal of the secondary hydroxyl function (Ph3P/CCl4/CH3CN; H2/Pd/C), reduction of the methyl ester (LiAlH4), and introduction of the exocyclic double bond (acetate pyrolysis, 550 °C) completes the synthesis of (±)-sinularene in 14 steps from cyclopentadiene. A parallel series of reactions employing the isopropyl epimer of 12 affords (±)-5-epi-sinularene.

Total synthesis of (±)-epithuriferic acid methyl ester via Diels–Alder reaction

2016 ◽  
Vol 14 (5) ◽  
pp. 1822-1830 ◽  
Author(s):  
Marek Koprowski ◽  
Piotr Bałczewski ◽  
Krzysztof Owsianik ◽  
Ewa Różycka-Sokołowska ◽  
Bernard Marciniak
Keyword(s):  
Methyl Ester ◽  
Total Synthesis ◽  
Acid Methyl Ester ◽  
Alder Reaction ◽  
Diels Alder ◽  
Natural Sources ◽  
Diels Alder Reaction ◽  
Acid Methyl

The first total synthesis of (±)-epithuriferic acid methyl ester from non-natural sources, in four steps (20% overall yield) is reported in this paper.

Intramolecular Diels-Alder Cycloadditions of cis-Cyclohexadienediols Derived Enzymatically from (2-Azidoethyl)benzene. Construction of Highly Functionalized Bridged Isoquinoline Synthons

2001 ◽  
Vol 66 (8) ◽  
pp. 1269-1286 ◽  
Author(s):  
Josef Zezula ◽  
Tomáš Hudlický ◽  
Ion Ghiviriga
Keyword(s):  
Methyl Ester ◽  
Maleic Anhydride ◽  
Total Synthesis ◽  
Organic Synthesis ◽  
Diels Alder

(3aR,7aS)-4-(2-Azidoethyl)-2,2-dimethyl-3a,7a-dihydrobenzo[1,3]dioxole (22) was converted in two steps to trienes23and24, which upon heating underwent intramolecular Diels-Alder reactions to give mixtures of isomeric 11,11-dimethyl-5-oxo-10,12-dioxa-4-azatetracyclo[6.5.2.01,6.09,13]pentadec-14-ene-7-carboxylates25,26and27,28, respectively. These products were separated and identified. For comparison, intermolecular Diels-Alder cycloaddition of diene22with maleic anhydride was carried out. Products of this reaction, 1-(2-azidoethyl)-4,4-dimethyl-3,5,10-trioxatetracyclo[5.5.2.02,6.08,12]tetradec-13-ene-9,11-diones (29and30) were converted to methyl ester analogues of31and32in a two-step sequence. The stereochemical outcome of these cycloadditions is discussed as well as their possible utilization in organic synthesis, especially in total synthesis of some alkaloids.

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