{"id":20095,"date":"2018-08-26T05:53:23","date_gmt":"2018-08-26T04:53:23","guid":{"rendered":"https:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=20095"},"modified":"2018-09-24T14:38:20","modified_gmt":"2018-09-24T13:38:20","slug":"organocatalytic-cyclopropanation-of-an-enal-computational-product-stereochemical-assignments","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=20095","title":{"rendered":"Organocatalytic cyclopropanation of an enal: (computational) product stereochemical assignments."},"content":{"rendered":"
\n

In the previous post<\/a>, I investigated the mechanism of cyclopropanation of an enal using a benzylic chloride using a quantum chemistry based procedure. Here I take a look at the NMR spectra of the resulting cyclopropane products, with an evaluation of the original stereochemical assignments.[1]<\/a><\/span><\/p>\n

\"\"<\/a><\/p>\n

Three products were identified, 4a-c <\/b>(aryl=2,4-dinitro)\u00a0with a fourth diastereomer undetected. The relative stereochemistries were assigned[1]<\/a><\/span> on the basis of NMR coupling constants, using the empirical Karplus or Bothner-By relationships. Here I calculate the NMR couplings at the B3LYP+GD3BJ\/Def2-TZVPP\/SCRF=chloroform level for a comparison, using a methyl group rather than the full n-heptyl one shown above.<\/p>\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n
\n

System, Data DOI<\/p>\n

10.14469\/hpc\/4650<\/a><\/p>\n<\/th>\n

Gibbs Energy<\/th>\nJ1(a)-2(b)<\/sub><\/th>\nJ1(a)-3(c)<\/sub><\/th>\n\n

J3(c)<\/sub>-2(b)<\/sub><\/p>\n<\/th>\n<\/tr>\n

4a (1S,2R,3R) expt (R-prolinol)<\/td>\n–<\/td>\n4.9<\/span><\/strong><\/td>\n9.0<\/span><\/strong><\/td>\n7.5<\/span><\/strong><\/td>\n<\/tr>\n
4a calc\u2021<\/sup><\/td>\n-910.861653<\/a><\/td>\n4.6<\/span><\/td>\n9.9<\/span><\/td>\n8.3<\/span><\/td>\n<\/tr>\n
-910.860816<\/a><\/td>\n4.4<\/span><\/td>\n10.7<\/span><\/td>\n7.9<\/span><\/td>\n<\/tr>\n
-910.859908<\/a><\/td>\n4.9<\/span><\/td>\n10.9<\/span><\/td>\n7.7<\/span><\/td>\n<\/tr>\n
-910.860299<\/a><\/td>\n5.2<\/span><\/td>\n8.1<\/span><\/td>\n8.1<\/span><\/td>\n<\/tr>\n
4b (1R,2R,3R) expt<\/td>\n–<\/td>\n9.6<\/span><\/strong><\/td>\n5.3<\/span><\/strong><\/td>\n6.7<\/span><\/strong><\/td>\n<\/tr>\n
4b calc<\/td>\n-910.859549<\/a><\/td>\n10.8<\/span><\/td>\n5.1<\/span><\/td>\n7.7<\/span><\/td>\n<\/tr>\n
4c (1S,2S,3R) expt<\/td>\n–<\/td>\n5.4<\/span><\/strong><\/td>\n5.4<\/span><\/strong><\/td>\n9.9<\/span><\/strong><\/td>\n<\/tr>\n
4c calc<\/td>\n-910.859820<\/a><\/td>\n4.2<\/span><\/td>\n5.5<\/span><\/td>\n10.4<\/span><\/td>\n<\/tr>\n
4d (1R,2S,3R) expt<\/td>\n–<\/td>\nn\/a<\/span><\/td>\n<\/tr>\n
4d calc<\/td>\n-910.855965<\/a><\/td>\n10.3<\/span><\/td>\n9.4<\/span><\/td>\n9.6<\/span><\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

The variation resulting from rotations about the substituents (the o-nitro and the carbaldehyde) as seen for 4a<\/strong> can be up to ~2 Hz. This could if needed be averaged by weighting with the Boltzmann populations. Even without this procedure one can see that for the three diastereomers where values were measured, the calculated couplings agree to 1 Hz or better. This provides confirmation of the original assignments. This quantum-based method can be used in cases where simple formulaic relationships may apply less well.<\/p>\n

\n

\u2021<\/sup>For four conformations, rotating the carbaldehyde and the o-nitro groups, as in red above.<\/p>\n

References<\/h2>\n
  1. M. Meazza, A. Kowalczuk, S. Watkins, S. Holland, T.A. Logothetis, and R. Rios, \"Organocatalytic Cyclopropanation of (<i>E<\/i>)-Dec-2-enal: Synthesis, Spectral Analysis and Mechanistic Understanding\", Journal of Chemical Education<\/i>, vol. 95, pp. 1832-1839, 2018. https:\/\/doi.org\/10.1021\/acs.jchemed.7b00566<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

    In the previous post, I investigated the mechanism of cyclopropanation of an enal using a benzylic chloride using a quantum chemistry based procedure. Here I take a look at the NMR spectra of the resulting cyclopropane products, with an evaluation of the original stereochemical assignments. Three products were identified, 4a-c (aryl=2,4-dinitro)\u00a0with a fourth diastereomer undetected. […]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"_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,"activitypub_content_warning":"","activitypub_content_visibility":"","activitypub_max_image_attachments":5,"activitypub_interaction_policy_quote":"anyone","activitypub_status":"","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},"jetpack_post_was_ever_published":false},"categories":[4],"tags":[2481,1395,2485,2486,1919,1705,1410,1785,2484],"ppma_author":[2661],"class_list":["post-20095","post","type-post","status-publish","format-standard","hentry","category-interesting-chemistry","tag-benzyl-group","tag-chemistry","tag-cyclopropanation","tag-cyclopropane-products","tag-cyclopropanes","tag-nuclear-magnetic-resonance","tag-organic-chemistry","tag-organic-reactions","tag-protecting-groups"],"yoast_head":"\nOrganocatalytic cyclopropanation of an enal: (computational) product stereochemical assignments. - Henry Rzepa's Blog<\/title>\n<meta name=\"robots\" content=\"index, follow, max-snippet:-1, max-image-preview:large, max-video-preview:-1\" \/>\n<link rel=\"canonical\" href=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=20095\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Organocatalytic cyclopropanation of an enal: (computational) product stereochemical assignments. - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"In the previous post, I investigated the mechanism of cyclopropanation of an enal using a benzylic chloride using a quantum chemistry based procedure. Here I take a look at the NMR spectra of the resulting cyclopropane products, with an evaluation of the original stereochemical assignments. Three products were identified, 4a-c (aryl=2,4-dinitro)\u00a0with a fourth diastereomer undetected. […]\" \/>\n<meta property=\"og:url\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=20095\" \/>\n<meta property=\"og:site_name\" content=\"Henry Rzepa's Blog\" \/>\n<meta property=\"article:published_time\" content=\"2018-08-26T04:53:23+00:00\" \/>\n<meta property=\"article:modified_time\" content=\"2018-09-24T13:38:20+00:00\" \/>\n<meta property=\"og:image\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2018\/08\/4a.svg\" \/>\n<meta name=\"author\" content=\"Henry Rzepa\" \/>\n<meta name=\"twitter:card\" content=\"summary_large_image\" \/>\n<meta name=\"twitter:label1\" content=\"Written by\" \/>\n\t<meta name=\"twitter:data1\" content=\"Henry Rzepa\" \/>\n\t<meta name=\"twitter:label2\" content=\"Estimated reading time\" \/>\n\t<meta name=\"twitter:data2\" content=\"1 minute\" \/>\n<!-- \/ Yoast SEO plugin. -->","yoast_head_json":{"title":"Organocatalytic cyclopropanation of an enal: (computational) product stereochemical assignments. - Henry Rzepa's Blog","robots":{"index":"index","follow":"follow","max-snippet":"max-snippet:-1","max-image-preview":"max-image-preview:large","max-video-preview":"max-video-preview:-1"},"canonical":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=20095","og_locale":"en_GB","og_type":"article","og_title":"Organocatalytic cyclopropanation of an enal: (computational) product stereochemical assignments. - Henry Rzepa's Blog","og_description":"In the previous post, I investigated the mechanism of cyclopropanation of an enal using a benzylic chloride using a quantum chemistry based procedure. Here I take a look at the NMR spectra of the resulting cyclopropane products, with an evaluation of the original stereochemical assignments. Three products were identified, 4a-c (aryl=2,4-dinitro)\u00a0with a fourth diastereomer undetected. […]","og_url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=20095","og_site_name":"Henry Rzepa's Blog","article_published_time":"2018-08-26T04:53:23+00:00","article_modified_time":"2018-09-24T13:38:20+00:00","og_image":[{"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2018\/08\/4a.svg","type":"","width":"","height":""}],"author":"Henry Rzepa","twitter_card":"summary_large_image","twitter_misc":{"Written by":"Henry Rzepa","Estimated reading time":"1 minute"},"schema":{"@context":"https:\/\/schema.org","@graph":[{"@type":"Article","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=20095#article","isPartOf":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=20095"},"author":{"name":"Henry Rzepa","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/#\/schema\/person\/2b40f7b9c872a4dc1547e040a11b6281"},"headline":"Organocatalytic cyclopropanation of an enal: (computational) product stereochemical assignments.","datePublished":"2018-08-26T04:53:23+00:00","dateModified":"2018-09-24T13:38:20+00:00","mainEntityOfPage":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=20095"},"wordCount":282,"commentCount":0,"image":{"@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=20095#primaryimage"},"thumbnailUrl":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2018\/08\/4a.svg","keywords":["Benzyl group","Chemistry","Cyclopropanation","cyclopropane products","Cyclopropanes","Nuclear magnetic resonance","Organic chemistry","Organic reactions","Protecting groups"],"articleSection":["Interesting chemistry"],"inLanguage":"en-GB","potentialAction":[{"@type":"CommentAction","name":"Comment","target":["https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=20095#respond"]}]},{"@type":"WebPage","@id":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=20095","url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=20095","name":"Organocatalytic cyclopropanation of an enal: (computational) product stereochemical assignments. - 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I had previously outlined a possible mechanistic route, identifying TS3 (below) as the first transition state in which C-C bond formation creates two chiral centres. This is followed by a lower energy\u00a0TS4 where\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2018\/09\/RSS-300x231.jpg?resize=350%2C200&ssl=1","width":350,"height":200},"classes":[]},{"id":20120,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=20120","url_meta":{"origin":20095,"position":1},"title":"Organocatalytic cyclopropanation of an enal: (computational) assignment of absolute configurations.","author":"Henry Rzepa","date":"September 1, 2018","format":false,"excerpt":"I am exploring the fascinating diverse facets of a recently published laboratory experiment for undergraduate students. Previously I looked at a possible mechanistic route for the reaction between an enal (a conjugated aldehyde-alkene) and benzyl chloride catalysed by base and a chiral amine, followed by the use of NMR coupling\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":19983,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=19983","url_meta":{"origin":20095,"position":2},"title":"Organocatalytic cyclopropanation of an enal: (computational) mechanistic understanding.","author":"Henry Rzepa","date":"August 25, 2018","format":false,"excerpt":"Symbiosis between computation and experiment is increasingly evident in pedagogic journals such as J. Chemical Education. Thus an example of original laboratory experiments, that later became twinned with a computational counterpart. So when I spotted this recent lab experiment I felt another twinning approaching. The reaction under consideration is that\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":10145,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=10145","url_meta":{"origin":20095,"position":3},"title":"Feist’s acid. Stereochemistry galore.","author":"Henry Rzepa","date":"April 4, 2013","format":false,"excerpt":"Back in the days (1893) when few compounds were known, new ones could end up being named after the discoverer. Thus Feist is known for the compound bearing his name; the 2,3 carboxylic acid of methylenecyclopropane (1, with Me replaced by CO2H). Compound 1 itself nowadays is used to calibrate\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"methylene-cyclopropane","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/04\/methylene-cyclopropane.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":14601,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=14601","url_meta":{"origin":20095,"position":4},"title":"Yes, no, yes. Computational mechanistic exploration of (nickel-catalysed) cyclopropanation using tetramethylammonium triflate.","author":"Henry Rzepa","date":"October 1, 2015","format":false,"excerpt":"A fascinating re-examination has appeared of a reaction first published in 1960 by Wittig and then repudiated by him in 1964 since it could not be replicated by a later student. According to the new work, the secret to a successful replication\u00a0seems to be\u00a0the presence of traces of a nickel\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":20601,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=20601","url_meta":{"origin":20095,"position":5},"title":"Impossible molecules.","author":"Henry Rzepa","date":"April 1, 2019","format":false,"excerpt":"Members of the chemical FAIR data community have just met in Orlando (with help from the NSF, the American National Science Foundation)\u00a0to discuss how such data is progressing in chemistry. There are a lot of themes converging at the moment. Thus this article extolls the virtues of having raw NMR\u2026","rel":"","context":"In "Chemical IT"","block_context":{"text":"Chemical IT","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=2"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]}],"jetpack_likes_enabled":false,"authors":[{"term_id":2661,"user_id":1,"is_guest":0,"slug":"admin","display_name":"Henry Rzepa","avatar_url":"https:\/\/secure.gravatar.com\/avatar\/897b6740f7f599bca7942cdf7d7914af5988937ae0e3869ab09aebb87f26a731?s=96&d=blank&r=g","0":null,"1":"","2":"","3":"","4":"","5":"","6":"","7":"","8":""}],"_links":{"self":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/20095","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=20095"}],"version-history":[{"count":24,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/20095\/revisions"}],"predecessor-version":[{"id":20249,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/20095\/revisions\/20249"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=20095"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=20095"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=20095"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=20095"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}