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totallymechanistic yet another chemistry blog totallymechanistic yet another chemistry blog neotripterifordin by corey liu posted january 5 2007 by totallymechanistic categories papers paul at chembark was writing that the aldrich catalog ranks 1 on my list of the top desk references of all time i agree it s a great help when looking for melting boiling points densities etc however i have a computer 2 meters from my hood and 1 meter from my desk so the sigma aldrich website is what i mostly use i also have another nice desk reference it s the total synthesis paper of neotripterifordin by corey and liu jacs 1997 119 9929 9930 actually my desk reference is the supporting information of that paper which is very well written and contains many common reactions the reactions on that paper are for example lialh4 reduction r oh r i wittig salt preparation wittig reaction acetylation deacetylation silyl protection deprotection mcpba oxidation thp protection deprotection mno2 oxidation katsuki sharpless epoxidation benzylation dess martin oxidation wolff kishner reduction oso4 oxidation pd c catalyzed hydrogenation birch reduction 2 2 cycloaddition ozone oxidation dibal h reduction barton mccombie reaction oh and this is how neotripterifordin looks like there is a nice cascade reaction in that synthesis interesting paper to read i recommend comments 10 comments still alive posted december 20 2006 by totallymechanistic categories news my apologies for the lack of posting flu or something kept me mostly horizontal for a few days then thanks to losing those precious days i was busy doing some reactions i wanted to get done before christmas it just feels nicer to go on a holiday when the intermediates are done and it s especially nicer to come back from a holiday when the intermediates are done and ready to be wasted in the next failing reaction well hope not purifying that 30 g by column chromatography was quite tedious and apologies also if someone s comment has not appeared in the comments i noticed that this thing has some kind of a spam filter installed by default i managed to unspam one of them sorry uncle al didn t mean to silence you but i m not quite sure if some comments were lost that s it for this post just wanted to let you know that this blog hasn t died in it s infancy it was just snoozing quietly more chemistry related posts coming soon comments 5 comments oddity 1 posted december 13 2006 by totallymechanistic categories oddities i ve got a new category again it s called oddities i will put there chemical stuff that i find odd weird surprising etc they probably aren t odd weird or surprising to many of you but they are something that made me go eh wtf this is the first oddities post the sulfone shown below is an intermediate i had during my project sorry for the mystical ar but i m just being extra cautious with any unpublished results the preparation of this intermediate was supposed to be fairly standard work with no surprises and so there i was sitting in the nmr room running a standard h nmr to verify that it s the right intermediate and as soon as i see the spectrum i go eh wtf now pause for a moment and think how you would expect the h nmr in d chloroform of that stuff to look like you can ignore the ar protons if you are thinking of something like two triplets 2h and 2h then you are thinking exactly what i was thinking however there s only one sharp singlet of 4 protons at around 4 ppm i was of course quite surprised to see the singlet so i ran a fast c nmr nothing weird there one peak at 57 ppm and another at 35 ppm after running some other experiments e g hsqc i was pretty convinced that the intermediate was ok eventually i changed the solvent to d6 dmso and there they were the triplets i m far from being an nmr expert so maybe one of you might want to explain the odd behavior in d chloroform comments 12 comments kharash sosnovsky allylic oxidation posted december 12 2006 by totallymechanistic categories name reactions today is the opening day of our new category name reactions here i m going to write about well name reactions i don t have any particular system how to choose the reactions but i ll concentrate on reactions that are not so well known i think most of my readers n 1 i know milo was here know so much about organic chemistry that featuring for example diels alder reaction would be just pointless today s name reaction is known as kharash sosnovsky allylic oxidation it was originally described by kharash and sosnovsky in jacs in 1958 doi link a more comprehensive study titled the copper catalyzed reaction of peresters with hydrocarbons was published 5 years later by walling and zavitsas in the same journal doi link below is one of the examples given by the gentlemen k and s themselves it might not be a wow that s amazing kind of reaction more like hmm interesting but quite nice considering that the selectivities are really good for example 1 hexene gives only hex 1 en 3 yl benzoate and none of the isomeric hex 2 en 1 yl benzoate how does that work i hear the audience scream well below is how the authors of the latter article say it works they have another option also for the last two steps where the radical r directly reacts with the benzoate anion that s it for today feel free to comment edit i replaced the links to pdfs with dois thanks to mitch from chemical forums for suggesting that comments 8 comments sodium borohydride iodine reduction posted december 11 2006 by totallymechanistic categories procedures lately i ve been doing quite a few asymmetric michael additions using a chiral oxazolidinone or one of the thio variants as a chiral auxiliary some of the auxiliaries are commercially available but far too expensive for my taste they can be easily synthesized from amino alcohols which are also commercially available but they too cost more then i m willing to pay so the only option is to make them myself which is not that bad a choice considering that the corresponding amino acids are not that expensive especially the l ones the d ones can be quite pricey this is how the auxiliaries look like there are many ways to reduce amino acids to amino alcohols but my favourite by far is sodium borohydride iodine combination pdf which is not only non expensive alternative but also convenient compared to for example lithium aluminum hydride see i don t like burning labs below is how it looks like chemically written so what is actually happening there this is how i understand it first iodine is reacting with one sodium borohydride so you get borane sodium iodide and hydrogen iodide then hydrogen iodide is reacting with another sodium borohydride so you get another borane and another sodium iodide plus some hydrogen all that borane is actually the stuff that reduces the acid to alcohol very nice and convenient i ve been doing it in 200 mmol scale and works just great giving the amino alcohol in good 70 yield after recrystallization from toluene that s it for today feel free to stop by again and comment if you like comments 58 comments and so it all began posted december 10 2006 by totallymechanistic categories news i know what you are thinking seriously is there really need for a new chemistry blog actually i don t know if you are thinking that but at least i was just a few hours ago i ve been an avid reader of chemistry blogs for months and now i just felt that i want to have my own so what will this blog be about to tell you the truth i don t know exactly generally spoken it will be about synthetic organic chemistry but what specifically that i don t know and what s with the name i m a big fan of total synthesis and if there wasn t the great site called totallysynthetic i would probably write a lot about total synthesis so i m a big fan of that site as you probably could have guessed from the name of this blog that s where the totally part comes from i m also really interested in reaction mechanisms i like knowing how things happen not just what happens so i was thinking that i want to write about reaction mechanisms and that s how i came up with the name totallymechanistic actually i think someone was suggesting that or something similar some time ago in totallysynthetic had i more imagination i might have come up with something more original but this will have to do at least for now i don t know exactly how often i will be posting but once a day is what i m aiming at see i don t know much yet but thank you for stopping by and welcome back i hope i ll have my first real post up by then comments 9 comments recent comments david on sodium borohydride iodine redu venkateswarlu on sodium borohydride iodine redu ralph on sodium borohydride iodine redu beau on sodium borohydride iodine redu soberme on sodium borohydride iodine redu recent posts neotripterifordin by corey liu still alive oddity 1 kharash sosnovsky allylic oxidation sodium borohydride iodine reduction categories name reactions news oddities papers procedures blogroll atom pushers anonymous chembark chemical chimera chemical forums chemical musings chemist in a transition state curly arrow in the pipeline kinasepro lamentations on chemistry molecule of the day org prep daily the chem blog the half decent pharmaceutical chemistry blog the sceptical chymist totally medicinal totally synthetic whistling in the wind journals angewandte chemie int ed chemistry a eur j j med chem jacs joc org lett archives january 2007 1 december 2006 5 meta create account log in entries feed comments feed wordpress com create a free website or blog at wordpress com subscribe subscribed totallymechanistic sign me up already have a wordpress com account log in now privacy totallymechanistic subscribe subscribed sign up log in report this content view site in reader manage subscriptions collapse this bar design a site like this with wordpress com get started