{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,5,12]],"date-time":"2026-05-12T00:26:13Z","timestamp":1778545573283,"version":"3.51.4"},"reference-count":40,"publisher":"Wiley","issue":"70","license":[{"start":{"date-parts":[[2023,11,2]],"date-time":"2023-11-02T00:00:00Z","timestamp":1698883200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2023,12,14]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Herein, we present previously unavailable C(sp<jats:sup>3<\/jats:sup>)\u2010rich polycyclic hydrocarbon scaffolds that have the potential to become valuable tools in medicinal chemistry and crop science as saturated bioisosteres of benzenoids. We have developed a scalable protocol (up to 50\u2005g from a single synthetic run) for the synthesis of tricyclo[3.3.0.0<jats:sup>3,7<\/jats:sup>]octane (bisnoradamantane or <jats:italic>stellane<\/jats:italic>) 1,5\u2010dicarboxylic acid derivatives. X\u2010ray crystallographic analysis of the stellane 1,5\u2010dicarboxylic acid dimethyl ester has revealed that this scaffold is an optimal saturated isostere for <jats:italic>ortho<\/jats:italic>\u2010disubstituted benzene where substituents exhibit in\u2010plane topology. The synthetic protocol is based on the oxidative cyclization of dimethyl octahydropentalene\u20102,5\u2010dicarboxylate (DMOD) through lithiation followed by I<jats:sub>2<\/jats:sub> oxidation. The reaction outcome is determined by the stereochemistry of the substrate. While the <jats:italic>endo,endo cis\u2010<\/jats:italic>DMOD, exclusively gives the \u201cunwanted\u201d Claisen cyclization product, the <jats:italic>exo,endo cis\u2010<\/jats:italic> and <jats:italic>exo,exo cis\u2010<\/jats:italic> stereoisomers afford the desired stellane 1,5\u2010dicarboxylic acid dimethyl ester quantitatively. DFT computations have revealed that the reaction proceeds via the dianion of dimethyl octahydropentalene\u20102,5\u2010dicarboxylate, which undergoes SET oxidation by I<jats:sub>2<\/jats:sub> to form a radical anion. The subsequent cyclization followed by a second SET oxidation gives the desired stellane derivative.<\/jats:p>","DOI":"10.1002\/chem.202302454","type":"journal-article","created":{"date-parts":[[2023,9,20]],"date-time":"2023-09-20T22:08:52Z","timestamp":1695247732000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":12,"title":["Multigram Synthesis of Dimethyl Stellane\u20101,5\u2010Dicarboxylate as a Key Precursor for <i>ortho<\/i>\u2010Benzene Mimics**"],"prefix":"10.1002","volume":"29","author":[{"given":"Oleh K.","family":"Smyrnov","sequence":"first","affiliation":[{"name":"Enamine Ltd  78 Winston Churchill Street Kyiv Ukraine"},{"name":"Taras Shevchenko National University of Kyiv  60 Volodymyrska Street Kyiv Ukraine"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Kostiantyn P.","family":"Melnykov","sequence":"additional","affiliation":[{"name":"Enamine Ltd  78 Winston Churchill Street Kyiv Ukraine"},{"name":"Taras Shevchenko National University of Kyiv  60 Volodymyrska Street Kyiv Ukraine"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Eduard B.","family":"Rusanov","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry National Academy of Sciences of Ukraine  Academik Kukhar Street 5 Kyiv Ukraine"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sergey Yu.","family":"Suikov","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry National Academy of Sciences of Ukraine  Academik Kukhar Street 5 Kyiv Ukraine"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Olexandr E.","family":"Pashenko","sequence":"additional","affiliation":[{"name":"Enamine Ltd  78 Winston Churchill Street Kyiv Ukraine"},{"name":"Taras Shevchenko National University of Kyiv  60 Volodymyrska Street Kyiv Ukraine"},{"name":"Institute of Organic Chemistry National Academy of Sciences of Ukraine  Academik Kukhar Street 5 Kyiv Ukraine"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Andrey A.","family":"Fokin","sequence":"additional","affiliation":[{"name":"Igor Sikorsky Kyiv Polytechnic Institute  37 Beresteiskyi Avenue Kyiv 03056 Ukraine"},{"name":"Institute of Organic Chemistry Justus Liebig University  Heinrich-Buff-Ring 17 35392 Giessen Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6519-1467","authenticated-orcid":false,"given":"Dmytro M.","family":"Volochnyuk","sequence":"additional","affiliation":[{"name":"Enamine Ltd  78 Winston Churchill Street Kyiv Ukraine"},{"name":"Taras Shevchenko National University of Kyiv  60 Volodymyrska Street Kyiv Ukraine"},{"name":"Institute of Organic Chemistry National Academy of Sciences of Ukraine  Academik Kukhar Street 5 Kyiv Ukraine"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4281-8268","authenticated-orcid":false,"given":"Serhiy V.","family":"Ryabukhin","sequence":"additional","affiliation":[{"name":"Enamine Ltd  78 Winston Churchill Street Kyiv Ukraine"},{"name":"Taras Shevchenko National University of Kyiv  60 Volodymyrska Street Kyiv Ukraine"},{"name":"Institute of Organic Chemistry National Academy of Sciences of Ukraine  Academik Kukhar Street 5 Kyiv Ukraine"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2023,11,2]]},"reference":[{"key":"e_1_2_10_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja02231a009"},{"key":"e_1_2_10_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527654307.ch1"},{"key":"e_1_2_10_3_1","unstructured":"\u00a0"},{"key":"e_1_2_10_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm901241e"},{"key":"e_1_2_10_5_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2md20347b"},{"key":"e_1_2_10_6_1","unstructured":"\u00a0"},{"key":"e_1_2_10_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201510675"},{"key":"e_1_2_10_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jmedchem.0c00746"},{"key":"e_1_2_10_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jmedchem.1c01215"},{"key":"e_1_2_10_10_2","doi-asserted-by":"publisher","DOI":"10.2174\/1573406418666220127124228"},{"key":"e_1_2_10_11_2","author":"Meanwell N. 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