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U of M CHEM 210 - Key 4

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I. (40 points)simeprevir(a) CIrcle all the tetrahedral (chiral) stereocenters in simeprevir and assign an appropriate (R or S) stereolabel.(b) Place a square around every individual ring that you would consider to be an aromatic system and write the number of p electrons contained within that system next to your square.hybridization electronic geometry observable geometryatom Oatom N133Name _______________________Page 1sp2sp2trigonal planartrigonal planarbenttrigonal planarall three answers must be right for the row = 3 no partialatom N23sp2trigonal planar bentatom C3sp3tetrahedral tetrahedralSimeprevir, trade name Olysio, is one of the newest and most effective drugs prescribed for the treatment and cure of chronic hepatitis C.NHONHSOONOOONOSNFor each of the atoms indicated with an arrow, provide the atom's most reasonable hybridization as well as its electronic geometry (VSEPR) and observable geometry (write none if it is not observable).RSRRR16HNONHSOONOOONOSNsimeprevirCON2N1Cl(Z)-1,5-dibromohept-5-en-1-yneConvert name to structure or structure to name as needed. Be sure to include all information on connectivity and stereochemistry in both your drawings and your naming.(R)-1-chloro-5-cyclopropylcyclopent-1-ene-if wrong connectivity: 0-if stereo is wrong but connectivity is right: 2(a) Name this compound:(b) Draw this compound:CBrBrA.B.C.662 pts each - 1 pt for circling, 1 pts for correct assignment2 pts for each square - 1 pt for finding, 1 pt for writing 6-1 pt each for circling or putting a square around any other sites-2 pts/ errorcarbons may be drawn in, could be bent to show connectivity - ignore this666Name _______________________Page 2II. (36 points)A.(S)(S)(S)(S)OOHNH3OHF4-fluorothreonine is an antibacterial compound made by Streptomyces cattleya. The compound is shown here in its fully protonated form.C1C2HO HHH3Nthe same molecule structural isomers enantiomersdiastereomersdifferent moleculesXX conformersThese drawings representOOHF(a) In the form and conformation shown,rotation of the C1-C2 bond is hindered by numerous intramolecular interactions. Draw a Newman projection of the C1-C2 bond in the conformation shown; view with the C1 in front, and Indicate all of the interactions that could inhibit bond rotation.N can donate two Hs, OH can only donate to the COOH (1 pt for all 3, no points if Hbond to C-H)(b) From the set of bases given in the box below, circle those bases that can deprotonate the most acidic proton on 4-fluorothreonine favorably (Keq > 1) without deprotonating the second most acidic proton favorably ( Keq <1), assuming that an excess of the base is available.NOOOOOH3CNHLiKNH3CH3CCH3CH3KO ONaBrNa66connectivity and stereo must be correct for first 3, conformation must be correct for 2 (5 pts)B.For each of the following pairs of drawings check all the descriptions that accurately apply.(S)(S)(S)(S)OOHNH3OHF(R)(R)(R)(R)OOHNH3OHFat least 1 R stereocenterX(S)(S)(S)(S)O(a)(b)4CH3H3COCH3CH3HHthe same molecule structural isomers enantiomersdiastereomersdifferent moleculesXX conformersThese drawings representat least 1 R stereocenter4the same molecule structural isomers enantiomersdiastereomersdifferent moleculesX conformersThese drawings representat least 1 R stereocenterX(c)(d)4OHCH3HHthe same molecule structural isomers enantiomersdiastereomersdifferent moleculesXX conformersThese drawings representat least 1 R stereocenter4the same molecule structural isomers enantiomersdiastereomersdifferent moleculesXX conformersThese drawings representat least 1 R stereocenterX(e)(f)4the same molecule structural isomers enantiomersdiastereomersdifferent moleculesXX conformersThese drawings representat least 1 R stereocenter4O(R)(R)O(S)(S)O(S)(S)O(R)(R)CH3OHHH(S)(S)(R)(R)OHCH3(R)(R)(S)(S)OHCH3(S)(S)(R)(R)(Z)(S)(S)(S)(S)(Z)X10.21517Name _______________________Page 3III. (35 points)Phenylboronic acid is stable to handle, yet reactive in a variety of different ways (Lewis acid AND Bronsted acid), making it a very useful reagent in organic synthesis. It is also used as a receptor for carbohydrates, and it is being studied for its potential cancer fighting therapeutic properties.BOPhOHBOOHHProvide an accurate and complete three-dimensional orbital picture for phenylboronic acid, considering all major resonance contributors when making your assessments about geometry. You should use lines, dashes, wedges, and p orbitals (lone or overlapping) to show the direction of all electrons (or empty orbitals) in your drawing. All bond angles should reflect the appropriate geometry and hybridization chosen for your drawing. NOTE: you may abbreviate the phenyl ring as "-Ph".ONHLiONH2Complete the following reactions, each of which involves phenylboronic acid. In all cases, provide all missing information; when more than one resonance contributor is possible in any answer you provide, draw the best.Keq =106-73take a rangeBOOH++pKa ~ 15LiHif pi bond is connected, charges must be assignedBOPhOHH93 pts/atomp orbital must be consistent with hybrid plane44BOOHPhenylboronic acidpKa = 8.83HBOOHH44BOOHHHONO2(1 equivalent)BOOHHOOCH3H3C(i) show the curved arrow mechanism for the most likely complexationBOOHHOOCH3H3Ceither O can carry the charge, but curved arrow mechanism must show the C=O O attackingBOOHHOOCH3H3Ceither one(ii) show product(s)Phenylboronic acid can undergo electrophilic aromatic substitutions. Using what you know about directing effects, predict the mononitration product(s). Briefly explain your answer using words and drawing(s).A.B.(a)(b) The missing molecules are anions; a counterion is provided.C.NOOBOOHHB is a meta director - open shell pulls electrons out of the ring, making O/P positions electrophilicBOOHHNOObetter the + here than next to the Bor(a) product(s)(b) briefly explain with drawing(s)34Name _______________________Page 4IV. (40 points)One Both NeitherWhich of these products is/are optically active? (check one)XIn this set of reaction predictions, it has already been determined that two different (but related) neutral organic products form (please ignore byproducts). Draw both products, clearly showing in your drawing all structural and/or stereochemical information that distinguishes them from each other. Then discuss the optical activity of these products and their relationship.enantiomersdiastereomersstructural isomersThese products are (check one):XH2 (excess)Pd422One Both NeitherWhich of these products is/are optically active? (check


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