{"id":14944,"date":"2015-11-28T18:32:03","date_gmt":"2015-11-28T18:32:03","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=14944"},"modified":"2015-11-30T06:20:34","modified_gmt":"2015-11-30T06:20:34","slug":"a-tutorial-problem-in-stereoelectronic-control-a-grob-alternative-to-the-tiffeneau-demjanov-rearrangement","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=14944","title":{"rendered":"A tutorial problem in stereoelectronic control. A Grob alternative to the Tiffeneau-Demjanov rearrangement?"},"content":{"rendered":"
\n

In answering tutorial problems, students often need skills in deciding how much time to spend on explaining what does not<\/strong> happen, as well as what does. Here I explore alternatives to the mechanism outlined in the previous post<\/a> to see what computation\u00a0has to say about what does (or might) not happen.<\/p>\n

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

I start with posing the question what does the chloride counter-ion do<\/em>? If you are aware of the literature on computational reaction mechanisms, you may note that where ionic species are involved, one of the ions is often excluded from the calculations. Here for example, the pertinent reacting species is a diazonium cation, but the anion would likely not be mentioned, and the calculation would be performed as a charged cation (the physically unrealistic charge=1 in the input file!). This is because of an awkward difficulty with ion-pairs. There is no formal bond between the two charged fragments\u00a0(unless a zwitterion) and so it is not entirely obvious quite where to place the counter-ion. In the diagram above, position\u00a01<\/strong> is where it was in my first exploration, but with knowledge that it might form a hydrogen bond to an acidic hydrogen, one could also perhaps place it into positions\u00a02<\/strong> or\u00a03<\/strong>. In 2<\/strong>, as shown by the blue arrows and product above, an entirely different reaction occurs known as the Grob fragmentation<\/em><\/strong>.[1]<\/a><\/span> In fact as a di-carbonyl compound, it can then participate in an acid-catalysed aldol condensation\u00a0and this can lead to the same product as the original\u00a0Tiffeneau-Demjanov rearrangement, albeit with loss of stereochemical integrity. So it might be\u00a0worth effort in explaining whether this alternative\u00a0is likely (in other words how robust the likely stereochemical integrity of the product is).<\/p>\n\n\n\n\n\n\n
System<\/th>\nRelative TS free energy<\/th>\nTS Dipole moment<\/th>\nDataDOI<\/th>\n<\/tr>\n
1<\/td>\n0.0<\/td>\n17.7<\/td>\n[2]<\/a><\/span><\/td>\n<\/tr>\n
2<\/td>\n1.4<\/td>\n24.2<\/td>\n[3]<\/a><\/span><\/td>\n<\/tr>\n
3<\/td>\n3.7<\/td>\n29.3<\/td>\n[4]<\/a><\/span><\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

The energies of the three located transition states increase with the dipole moment; as the counter-ion moves further from the positive charge, its position becomes less stable. Still, route 2 is not that much higher in energy. Time for an IRC (intrinsic reaction coordinate) to explore what actually does happen during route 2, the possible Grob rearrangement.<\/p>\n

\"grob1\"<\/a><\/p>\n

The reaction animation above shows the required Grob characteristic, the green bond breaking. But instead of the OH then de-protonating, the hydrogen stays in place and instead the\u00a0Tiffeneau-Demjanov migration takes place. This will require removal of a different proton and indeed in the latter stages, the chloride anion starts off in its determined journey to do so.<\/p>\n

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

The variation in dipole moment as the reaction proceeds is fascinating. At IRC -6, it reaches a minimum, but then reverses itself in hunt of a better way of reducing the dipole moment.<\/p>\n

What about 3? This is slightly artificial, since the real system has a methoxy group here, which would inhibit this route. One can still learn chemistry though. The hydrogen bond formed from chloride to the OH encourages the anomeric effect to form a partial oxy-anion, which in turn encourages the red bond to break rather than the green one. But in fact no complete proton transfer happens, and the reaction reaches a non-productive cul-de-sac.\u00a0<\/p>\n

\"Alt1\"<\/a><\/p>\n

So, to conclude, there is no Grob fragmentation! Instead, a slightly confused\u00a0Tiffeneau-Demjanov migration occurs in a rather more roundabout manner than previously. We have explored here just TWO reaction trajectories. A more statistical exploration of the trajectory landscape will give us a more complete picture, but I rather fancy that would be very well above the call of duty required to answer a stereochemical problem!<\/p>\n

References<\/h2>\n
  1. C.A. Grob, and W. Baumann, \"Die 1,4\u2010Eliminierung unter Fragmentierung\", Helvetica Chimica Acta<\/i>, vol. 38, pp. 594-610, 1955. https:\/\/doi.org\/10.1002\/hlca.19550380306<\/a>\n\n<\/li>\n
  2. H.S. Rzepa, \"C 8 H 13 Cl 1 N 2 O 4\", 2015. https:\/\/doi.org\/10.14469\/ch\/191653<\/a>\n\n<\/li>\n
  3. H.S. Rzepa, \"C 8 H 13 Cl 1 N 2 O 4\", 2015. https:\/\/doi.org\/10.14469\/ch\/191654<\/a>\n\n<\/li>\n
  4. H.S. Rzepa, \"C 8 H 13 Cl 1 N 2 O 4\", 2015. https:\/\/doi.org\/10.14469\/ch\/191655<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

    In answering tutorial problems, students often need skills in deciding how much time to spend on explaining what does not happen, as well as what does. Here I explore alternatives to the mechanism outlined in the previous post to see what computation\u00a0has to say about what does (or might) not happen. I start with posing […]<\/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":[152,1402,832,1596,24,1594,1595],"ppma_author":[2661],"class_list":["post-14944","post","type-post","status-publish","format-standard","hentry","category-interesting-chemistry","tag-animation","tag-chemical-bond","tag-condensation","tag-demjanov-rearrangement","tag-energy","tag-rearrangement-reactions","tag-tiffeneau-demjanov-rearrangement"],"yoast_head":"\nA tutorial problem in stereoelectronic control. A Grob alternative to the Tiffeneau-Demjanov rearrangement? - 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=14944\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"A tutorial problem in stereoelectronic control. A Grob alternative to the Tiffeneau-Demjanov rearrangement? - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"In answering tutorial problems, students often need skills in deciding how much time to spend on explaining what does not happen, as well as what does. Here I explore alternatives to the mechanism outlined in the previous post to see what computation\u00a0has to say about what does (or might) not happen. 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The monoprotonated mechanism.","author":"Henry Rzepa","date":"January 8, 2013","format":false,"excerpt":"Eagle-eyed footnote readers might have spotted one at the bottom of the post on the benzidine rearrangement. I was comparing the N-N bond lengths in crystal structures of known diprotonated hydrazines (~1.45\u00c5) with the computed N-N bond length at the start point of the intrinsic reaction coordinate for the [5,5]\u2026","rel":"","context":"In \"free energy barrier\"","block_context":{"text":"free energy barrier","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?tag=free-energy-barrier"},"img":{"alt_text":"Transition state between p-complex and N-N diprotonated diphenyhydrazine. 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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":9186,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9186","url_meta":{"origin":14944,"position":3},"title":"The \u03c0-complex in the benzidine rearrangement: a molecular orbital analysis.","author":"Henry Rzepa","date":"January 18, 2013","format":false,"excerpt":"Michael Dewar famously implicated a so-called\u00a0\u03c0-complex in the benzidine rearrangement, back in the days when quantum mechanical calculations could not yet provide a quantitatively accurate reality check. Because this\u00a0\u03c0-complex actually remains a relatively unusual species to encounter in day-to-day chemistry, I thought I would try to show in a simple\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":7434,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=7434","url_meta":{"origin":14944,"position":4},"title":"The Curtius rearrangement. One step or two?","author":"Henry Rzepa","date":"August 6, 2012","format":false,"excerpt":"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\u2026","rel":"","context":"In \"elimination\"","block_context":{"text":"elimination","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?tag=elimination"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2012\/08\/curtius_Small.gif?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":9105,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9105","url_meta":{"origin":14944,"position":5},"title":"The Benzidine rearrangement. Computed kinetic isotope effects.","author":"Henry Rzepa","date":"January 11, 2013","format":false,"excerpt":"Kinetic isotope effects have become something of a lost art when it comes to exploring reaction mechanisms. But in their heyday they were absolutely critical for establishing the mechanism of the benzidine rearrangement. This classic mechanism proceeds via bisprotonation of diphenyl hydrazine, but what happens next was the crux. Does\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":[]}],"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\/14944","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=14944"}],"version-history":[{"count":13,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/14944\/revisions"}],"predecessor-version":[{"id":14963,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/14944\/revisions\/14963"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=14944"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=14944"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=14944"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=14944"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}