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.

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.

Recent advances in the application of Diels–Alder reactions involving o-quinodimethanes, aza-o-quinone methides and o-quinone methides in natural product total synthesis

2018 ◽  
Vol 47 (21) ◽  
pp. 7926-7953 ◽  
Author(s):  
Baochao Yang ◽  
Shuanhu Gao
Keyword(s):  
Total Synthesis ◽  
Natural Product ◽  
Organic Synthesis ◽  
Diels Alder ◽  
Quinone Methides ◽  
Recent Advances

This review summarizes recent advances in Diels–Alder reactions involving o-QDMs, o-QMs and aza-o-QMs. The power and potential of this strategy in organic synthesis and natural product total synthesis is highlighted.

scholarly journals Recent applications of intramolecular Diels–Alder reaction in total synthesis of natural products

RSC Advances ◽  
2015 ◽  
Vol 5 (63) ◽  
pp. 50890-50912 ◽  
Author(s):  
Majid M. Heravi ◽  
Vaezeh Fathi Vavsari
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Organic Synthesis ◽  
Cycloaddition Reaction ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction

Diels–Alder (D–A) reaction is undoubtedly the most powerful [4 + 2] cycloaddition reaction in organic synthesis.

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