STEREOCONTROLLED INTRAMOLECULAR IRON-MEDIATED DIENE/OLEFIN CYCLIZATION
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Case Western Reserve University School of Graduate Studies / OhioLINK
2015
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| Online Access: | http://rave.ohiolink.edu/etdc/view?acc_num=case1436355959 |
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ndltd-OhioLink-oai-etd.ohiolink.edu-case14363559592021-08-03T06:31:53Z STEREOCONTROLLED INTRAMOLECULAR IRON-MEDIATED DIENE/OLEFIN CYCLIZATION Zhang, Sheng Chemistry Intramolecular iron-mediated diene/olefin cyclocoupling reactions using vinyl ethers as the olefin partners have been investigated. Spirolactams with functionalized (alkoxymethyl) side chains can be formed under thermal conditions with high yields. Introduction of a methoxy group at the C3 position allowed the formation of one single diastereomer after the demetallation and hydrolysis of the cyclized products.An iron mediated tandem double [6+2] ene-type cyclization reaction has been expanded using a dienol ether as the pendant diene, resulting in a spirotricyclic molecule that has alkoxymethyl functionality at the cyclization terminus. Competing [4+4] cycloaddition that occurs during the thermally activated reaction can be ameliorated by using a photochemical procedure at moderately elevated temperature.Alkylation reaction of an ester containing iron tricarbonyl moiety has been found to be stereoselective during the approach towards synthesis of hispidospermidin’s spirocyclic core. The stereocontrol is resulting from the adjacent iron tricarbonyl group during the enolate alkylation process, which was shown by the crystal structure of the alkylation product, which was further converted to a substrate that can potentially undergo spirocyclization. Another all-carbon substrate was synthesized to test a one-pot all-carbon cyclization. Preliminary attempts cyclizing both substrates were not successful. 2015-09-03 English text Case Western Reserve University School of Graduate Studies / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=case1436355959 http://rave.ohiolink.edu/etdc/view?acc_num=case1436355959 unrestricted This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws. |
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NDLTD |
| language |
English |
| sources |
NDLTD |
| topic |
Chemistry |
| spellingShingle |
Chemistry Zhang, Sheng STEREOCONTROLLED INTRAMOLECULAR IRON-MEDIATED DIENE/OLEFIN CYCLIZATION |
| author |
Zhang, Sheng |
| author_facet |
Zhang, Sheng |
| author_sort |
Zhang, Sheng |
| title |
STEREOCONTROLLED INTRAMOLECULAR IRON-MEDIATED DIENE/OLEFIN CYCLIZATION |
| title_short |
STEREOCONTROLLED INTRAMOLECULAR IRON-MEDIATED DIENE/OLEFIN CYCLIZATION |
| title_full |
STEREOCONTROLLED INTRAMOLECULAR IRON-MEDIATED DIENE/OLEFIN CYCLIZATION |
| title_fullStr |
STEREOCONTROLLED INTRAMOLECULAR IRON-MEDIATED DIENE/OLEFIN CYCLIZATION |
| title_full_unstemmed |
STEREOCONTROLLED INTRAMOLECULAR IRON-MEDIATED DIENE/OLEFIN CYCLIZATION |
| title_sort |
stereocontrolled intramolecular iron-mediated diene/olefin cyclization |
| publisher |
Case Western Reserve University School of Graduate Studies / OhioLINK |
| publishDate |
2015 |
| url |
http://rave.ohiolink.edu/etdc/view?acc_num=case1436355959 |
| work_keys_str_mv |
AT zhangsheng stereocontrolledintramolecularironmediateddieneolefincyclization |
| _version_ |
1719438463180210176 |