{"id":4260,"date":"2024-01-08T11:25:40","date_gmt":"2024-01-08T09:25:40","guid":{"rendered":"https:\/\/ospt.osi.lv\/?p=4260"},"modified":"2024-01-08T11:25:40","modified_gmt":"2024-01-08T09:25:40","slug":"chiral-4-meo-pyridine-mopy-catalyst-for-enantioselective-cyclopropanation-attenuation-of-lewis-basicity-leads-to-improved-catalytic-efficiency-2","status":"publish","type":"post","link":"https:\/\/ospt.osi.lv\/chiral-4-meo-pyridine-mopy-catalyst-for-enantioselective-cyclopropanation-attenuation-of-lewis-basicity-leads-to-improved-catalytic-efficiency-2\/","title":{"rendered":"51. Chiral 4-MeO-Pyridine (MOPY) Catalyst for Enantioselective Cyclopropanation: Attenuation of Lewis Basicity Leads to Improved Catalytic Efficiency"},"content":{"rendered":"<div class=\"wpb-content-wrapper\"><p>[vc_row][vc_column][vc_column_text]Kluga R., Kinens A., Suna E. <em><span dir=\"ltr\">Chem. Eur. J. <\/span><\/em><strong><span dir=\"ltr\">2024<\/span><\/strong>, e202301136<br \/>\nDOI: <a title=\"Chiral 4-MeO-Pyridine (MOPY) Catalyst for Enantioselective Cyclopropanation: Attenuation of Lewis Basicity Leads to Improved Catalytic Efficiency\" href=\"https:\/\/doi.org\/10.1002\/chem.202301136\" target=\"_blank\" rel=\"nofollow noopener\">10.1002\/chem.202301136<\/a>.<\/p>\n<p>&nbsp;<\/p>\n<p><!--more--><\/p>\n<h4>Abstract<\/h4>\n<p style=\"text-align: justify;\"><span dir=\"ltr\">The design of pyridine<\/span><span dir=\"ltr\">&#8211;<\/span><span dir=\"ltr\">derived organocatalysts aims at the <\/span><span dir=\"ltr\">increase of their Lewis basicity, however such an approach is not <\/span><span dir=\"ltr\">always <\/span><span dir=\"ltr\">efficient<\/span><span dir=\"ltr\">. For example, s<\/span><span dir=\"ltr\">trongly Lewis basic DMAP is <\/span><span dir=\"ltr\">completely inefficient <\/span><span dir=\"ltr\">as catalyst <\/span><span dir=\"ltr\">in the cyclopropanation reaction. <\/span><span dir=\"ltr\">Herein we disclose an alternative approach that relies on attenuation <\/span><span dir=\"ltr\">of DMAP Lewis basicity. Specifically, the replacement of 4<\/span><span dir=\"ltr\">&#8211;<\/span><span dir=\"ltr\">dimethylamino substituent in DMAP for 4<\/span><span dir=\"ltr\">&#8211;<\/span><span dir=\"ltr\">MeO group delivered a <\/span><span dir=\"ltr\">highly efficient catalyst for <\/span><span dir=\"ltr\">cyclopropanation of electron<\/span><span dir=\"ltr\">&#8211;<\/span><span dir=\"ltr\">defici<\/span><span dir=\"ltr\">ent <\/span><span dir=\"ltr\">olefins <\/span><span dir=\"ltr\">with <\/span><span dir=\"ltr\">\u03b1-<\/span><span dir=\"ltr\">bromoketones. <\/span><span dir=\"ltr\">K<\/span><span dir=\"ltr\">inetic studies provide compelling <\/span><span dir=\"ltr\">evidence that the superior catalytic efficiency of 4<\/span><span dir=\"ltr\">&#8211;<\/span><span dir=\"ltr\">MeO pyridine <\/span><span dir=\"ltr\">(MOPY) is to be attributed to the favorable balance between Lewis <\/span><span dir=\"ltr\">basicity and leaving group ability. The use of chiral, e<\/span><span dir=\"ltr\">nantiomerically <\/span><span dir=\"ltr\">pure MOPY catalyst has helped to achieve high enantioselectivities <\/span><span dir=\"ltr\">(up to 91:9 er) in the previously unreported pyridine<\/span><span dir=\"ltr\">&#8211;<\/span><span dir=\"ltr\">catalyzed <\/span><span dir=\"ltr\">cyclopropanation reaction.<\/span><\/p>\n<p>[\/vc_column_text][\/vc_column][\/vc_row]<\/p>\n<\/div>","protected":false},"excerpt":{"rendered":"<p>[vc_row][vc_column][vc_column_text]Kluga R., Kinens A., Suna E. Chem. Eur. J. 2024, e202301136 DOI: 10.1002\/chem.202301136. &nbsp;<\/p>\n","protected":false},"author":5,"featured_media":4231,"comment_status":"closed","ping_status":"open","sticky":false,"template":"","format":"image","meta":{"_exactmetrics_skip_tracking":false,"_exactmetrics_sitenote_active":false,"_exactmetrics_sitenote_note":"","_exactmetrics_sitenote_category":0,"footnotes":""},"categories":[45,16],"tags":[],"aioseo_notices":[],"_links":{"self":[{"href":"https:\/\/ospt.osi.lv\/wp-json\/wp\/v2\/posts\/4260"}],"collection":[{"href":"https:\/\/ospt.osi.lv\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/ospt.osi.lv\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/ospt.osi.lv\/wp-json\/wp\/v2\/users\/5"}],"replies":[{"embeddable":true,"href":"https:\/\/ospt.osi.lv\/wp-json\/wp\/v2\/comments?post=4260"}],"version-history":[{"count":1,"href":"https:\/\/ospt.osi.lv\/wp-json\/wp\/v2\/posts\/4260\/revisions"}],"predecessor-version":[{"id":4261,"href":"https:\/\/ospt.osi.lv\/wp-json\/wp\/v2\/posts\/4260\/revisions\/4261"}],"wp:featuredmedia":[{"embeddable":true,"href":"https:\/\/ospt.osi.lv\/wp-json\/wp\/v2\/media\/4231"}],"wp:attachment":[{"href":"https:\/\/ospt.osi.lv\/wp-json\/wp\/v2\/media?parent=4260"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/ospt.osi.lv\/wp-json\/wp\/v2\/categories?post=4260"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/ospt.osi.lv\/wp-json\/wp\/v2\/tags?post=4260"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}