{"id":7434,"date":"2012-08-06T14:01:21","date_gmt":"2012-08-06T13:01:21","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=7434"},"modified":"2012-08-06T14:01:21","modified_gmt":"2012-08-06T13:01:21","slug":"the-curtius-rearrangement-one-step-or-two","status":"publish","type":"post","link":"https:\/\/www.rzepa.net\/blog\/?p=7434","title":{"rendered":"The Curtius rearrangement. One step or two?"},"content":{"rendered":"
\n

The Curtius reaction is represented in most chemistry texts and notes as following path (a) below. It is one of a general class of thermally induced rearrangement which might be described as elimination\/migration (in a sense similar to this ring contraction migration\/elimination<\/a>), in this case implicating a nitrene intermediate if the two steps occur consecutively. Wikipedia is normally very much on the ball with this sort of thing, and a comment about the reaction mechanism<\/a> there notes that current evidence prefers route (b), avoiding nitrene intermediacy (and hence formally removing this from examples of nitrene reactions).<\/p>\n

\"\"<\/p>\n

So time for a reality check (which in this case takes the form of a \u03c9B97XD\/6-311G(d,p)\/SCRF=dichloromethane calculation).\u00a0<\/p>\n

\"\"<\/p>\n

\"\"<\/p>\n

\"\"<\/p>\n

This is pretty clear-cut; no nitrene intermediate. Now for the standard text-books to catch up!<\/p>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

The Curtius reaction is represented in most chemistry texts and notes as following path (a) below. It is one of a general class of thermally induced rearrangement which might be described as elimination\/migration (in a sense similar to this ring contraction migration\/elimination), in this case implicating a nitrene intermediate if the two steps occur consecutively. […]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"jetpack_post_was_ever_published":false,"_jetpack_newsletter_access":"","_jetpack_dont_email_post_to_subs":false,"_jetpack_newsletter_tier_id":0,"_jetpack_memberships_contains_paywalled_content":false,"_jetpack_memberships_contains_paid_content":false,"footnotes":"","jetpack_publicize_message":"","jetpack_publicize_feature_enabled":true,"jetpack_social_post_already_shared":true,"jetpack_social_options":{"image_generator_settings":{"template":"highway","default_image_id":0,"font":"","enabled":false},"version":2}},"categories":[1],"tags":[895,897,1529,1530,1527],"class_list":["post-7434","post","type-post","status-publish","format-standard","hentry","category-uncategorized","tag-elimination","tag-migration","tag-pericyclic","tag-reaction-mechanism","tag-tutorial-material"],"jetpack_publicize_connections":[],"jetpack_featured_media_url":"","jetpack_sharing_enabled":true,"jetpack_shortlink":"https:\/\/wp.me\/p1gPyz-1VU","jetpack_likes_enabled":true,"_links":{"self":[{"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=\/wp\/v2\/posts\/7434","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=7434"}],"version-history":[{"count":0,"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=\/wp\/v2\/posts\/7434\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=7434"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=7434"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.rzepa.net\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=7434"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}