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

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Title:Intramolecular Diels-Alder Cycloadditions of cis-Cyclohexadienediols Derived Enzymatically from (2-Azidoethyl)benzene. Construction of Highly Functionalized Bridged Isoquinoline Synthons
Creators:
Zezula, Josef
Hudlický, Tomáš
Ghiviriga, Ion
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 66, 8, pp. 1269-1286
Uncontrolled Keywords:Chemoenzymatic synthesis, Morphine, Total syntheses, Biotransformations, Diels-Alder reactions, Isoquinoline alkaloids, Asymmetric synthesis, Bridged octahydroisoquinolones

Abstract

(3a<i>R</i>,7a<i>S</i>)-4-(2-Azidoethyl)-2,2-dimethyl-3a,7a-dihydrobenzo[1,3]dioxole (<strong>22</strong>) was converted in two steps to trienes <strong>23</strong> and <strong>24</strong>, which upon heating underwent intramolecular Diels-Alder reactions to give mixtures of isomeric 11,11-dimethyl-5-oxo-10,12-dioxa-4-azatetracyclo[6.5.2.0<sup>1,6</sup>.0<sup>9,13</sup>]pentadec-14-ene-7-carboxylates <strong>25</strong>, <strong>26</strong> and <strong>27</strong>, <strong>28</strong>, respectively. These products were separated and identified. For comparison, intermolecular Diels-Alder cycloaddition of diene <strong>22</strong> with maleic anhydride was carried out. Products of this reaction, 1-(2-azidoethyl)-4,4-dimethyl-3,5,10-trioxatetracyclo[5.5.2.0<sup>2,6</sup>.0<sup>8,12</sup>]tetradec-13-ene-9,11-diones (<strong>29</strong> and <strong>30</strong>) were converted to methyl ester analogues of <strong>31</strong> and <strong>32</strong> in 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. <p>

Title:Intramolecular Diels-Alder Cycloadditions of cis-Cyclohexadienediols Derived Enzymatically from (2-Azidoethyl)benzene. Construction of Highly Functionalized Bridged Isoquinoline Synthons
Creators:
Zezula, Josef
Hudlický, Tomáš
Ghiviriga, Ion
Uncontrolled Keywords:Chemoenzymatic synthesis, Morphine, Total syntheses, Biotransformations, Diels-Alder reactions, Isoquinoline alkaloids, Asymmetric synthesis, Bridged octahydroisoquinolones
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:66
Number:8
Page Range:pp. 1269-1286
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20011269UNSPECIFIED
ID Code:1856
Item Type:Article
Deposited On:06 Feb 2009 17:13
Last Modified:06 Feb 2009 16:13

Citation

Zezula, Josef; Hudlický, Tomáš; Ghiviriga, Ion (2001) Intramolecular Diels-Alder Cycloadditions of cis-Cyclohexadienediols Derived Enzymatically from (2-Azidoethyl)benzene. Construction of Highly Functionalized Bridged Isoquinoline Synthons. Collection of Czechoslovak Chemical Communications, 66 (8). pp. 1269-1286. ISSN 0010-0765

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