1 of 9 Final Exam [Chapters 1-10, 14 (Carey textbook)] CHE201/CHE203A-C Professor Diver and Dr. Clizbe Dec 13, 2014 Fall 2014 Version A (Exam duration: 3 h) Last Name: First Name: circle one: Dr. Clizbe or Dr. Diver and: Section ( A, B, C ) TA Name:____________________________ or CHE203 Page Total Possible Points (Possible Points per page) Points 2 30 3 30 4 30 5 25 + 5 extra 6 25 + 3 extra 7 30 8 30 9 Periodic Table TOTAL POSSIBLE: 208 YOUR TOTAL:_________ Molecular models are ALLOWED; calculators are NOT ALLOWED. No cell phones or extra paper will be provided. Fill out the exam in pen, use the back of the page if more room is needed. CHECK THAT YOUR EXAM INCLUDES ALL 9 PAGES.2 of 9 1. (60 pts) Provide the short answer or circle the molecule where appropriate. Circle the correct structure for each question. (12 x 5 pts each). a. Circle the molecule with the highest heat of hydrogenation. b. Circle the molecule that is meso (circle all that apply). BrBrCH3ClHCH2CH3ClClClClClCl c. Circle the molecule that is identical to the molecule A drawn in the box BrClCH3Br HClHCH2CH3CH3Br HHClCH2CH3CH3H BrClHCH2CH3CH3H BrHClCH2CH3A d. Provide an example of an allene: e. Draw the most stable chair conformation of trans-1,2-dichlorocyclohexane: f. Circle the molecule with the highest boiling point (bp): OHOOHO3 of 9 g. Circle the dienophile which is MOST REACTIVE in the Diels-Alder reaction: ClOOOOCH3H3COOCH3OCH3 h. Circle the least stable gauche conformation: CH3HHHHCH3HCH3CH3CH3HCH3HCH3CH3CH3CH3HHCH3CH3HHHHCH3CH3HCH3CH3 i. Bromination (Br2 in CCl4) of an alkene gave a single diastereomer shown. What was the structure of the alkene? (provide structureof the alkene)Br2 CCl4CH3H BrH BrCH3 j. Circle the alkane that will give a single monochlorination product (Cl2, hv): k. Circle the base capable of completely deprotonating propyne (CH3CH2CCH) (circle all that apply): KOHKOt-BupyridineNaNH2KFPd(PPh3)4N l. Circle the molecule with the (2S, 3R) configuration: OHClOHClOHClOHClOHCl4 of 9 2. (30 pts) Predict the products or each reaction. If multiple products are formed indicate which is major and minor. For full credit, you must show stereochemistry where appropriate. (6 x 5 pts each) NRuPhCy3PCy3PClClGrubbs' cat.TsOHPh1) pTsCl, pyridine2) CH3CO2NaPhOCH3OCH3CH2MgBr (excess)Et2OHCl (1 equiv)OHBr2NaHCO3/CH2Cl2C6H11BrOBrKOt-Bu5 of 9 3. (25 pts) Consider the following reaction: ClH3O+ClHO (a) Provide a detailed, electron-pushing mechanism to explain the formation of the product shown. Use the arrow formalism and be sure all steps are charge- and mass-balanced (15 points). (b) (5 pts) A minor amount of another substitution product was also formed. What is it? (c) (5 pts) When optically active A is used in the reaction, what is the expected optical activity of the product? ClA [α]D25 + 9.3 (d) (extra 5 pts) Another minor product B was also found. How was it formed? OHClminor by product B6 of 9 4. (25 pts) Consider the following cross coupling reaction: Br+B(OH)2Pd(PPh3)4 (cat.)KOH+ KBr + B(OH)3CROSS COUPLING REACTION: (a) (15 pts) Below, the catalytic cycle is shown for this Pd catalyzed cross coupling reaction. In boxes a-c, indicate the type of basic step (choices: reduction, electron transfer, oxidative addition, reductive elimination, isomerization, β-hydride elimination or transmetallation). Provide structures for intermediates A and B, showing all ligands present on the Pd atom. Pd(PPh3)2Pd(PPh3)4- 2 PPh3active catalystBrPdPdB(OH)2intermediate Aintermediate BKBr+ B(OH)3CATALYTIC CYCLE:(a)(b)(c)+ KOH (b) (5 pts) Using electron counting rules for metal complexes, how many valence electrons are present in the active Pd catalyst, Pd(PPh3)2? (c) (5 pts) What is the oxidation state of the Pd atom in intermediate A? (d) (extra 3 pts) What is the name of the reaction in (a)? ____________________Hint: he won a Nobel Prize in Chemistry.7 of 9 5. (30 pts) Propose a synthesis of each molecule based on the specified starting materials. Your answer should give forward synthesis steps in the proper order to obtain the targeted structure. (a) (15 pts) OHfrom acetylene andOCH3H (b) (15 pts) Br PhfromClandO8 of 9 6. (30 pts) Provide the chemical reagents needed to bring about each of the reactions depicted below, in good chemical yield. In some cases two or three steps might be needed. You do not need to specify solvents (5 x 6 pts each). BrOH SCH3HOBrBr9 of 9 Fr87francium223.01973 45678 9 101112Cs55cesium132.9054Rb37rubidium85.4678K19potassium39.0983Na11sodium22.9897Li3lithium6.941H1hydrogen1.00794226.0254Ba56barium137.327Sr38strontium87.67Ca20calcium40.078Mg12magnesium24.3056Be4berylium9.01218Ac59227.0278La57138.9055Y3985.4678Sc2144.9559Raradium58104724022TiV Cr Mn Fe Co Ni Cu Zn23 24 25 26 27 28 29 30scandiumtitanium vanadium chromiummanganeseiron cobalt nickelcopperzinc47.88 50.9415 51.9961 54.9381 55.847 58.933254.6963.546 65.39ZrNb Mo Tc Ru Rh Pd Ag Cd41 42 43 44 45 46 47 48zirconiummolybdenumtechnetium ruthenium rhodiumpalladiumsilver cadmium91.244 92.9064 95.94 98.9063 101.07 102.9055 106.42 107.8682 112.411HfTa W ReOsIr Pt AuHg73 74 75 76 77 78 79 80hafnium tantalum tungstenrheniumosmium iridium platinumgoldmercury178.49 180.9479 183.85 186.207 190.2 192.22 195.08 196.96654 200.59niobiumyttriumlanthanumB C N O F Ne5 6 7 8910boron carbon nitrogenoxygen fluorineneon10.811 12.011 14.00674 15.9994 18.9984032 20.1797Al Si P S Cl Ar13 14 15 161718aluminumsiliconphosphorussulfur chlorineargon26.981539 28.0855 30.97376 32.066 35.4527 3 9.948Ga Ge As Se Br Kr31 32 33 343536galiumgermanium arsenicselenium brominekrypton69.723 72.61 74.92159 78.96 79.904 83.80InSn Sb Te I Xe49 50 51 525354indiumtinantimonytellurium iodinexenon114.82 118.71 121.75 127.6 126.904 131.29Tl Pb Bi Po At Rn81 82 83 848586thallium lead bismuthpolonium astatineradon204.3833 207.6 208.9804 208.98 209.987 222.0176He2helium4.002602actiniumTh90thorium232.0381Ce58cerium140.115Pa91231.0359Pr59140.907659260Nd PmSmEuGdTbDyHo Er61 62 63 64 65 66 67 68praseodymiumneodymiumpromethiumsamariumeuropiumgadoliniumterbiumdysprosiumerbium144.24 146.9151 150.36 151.965 157.25 158.925 162.50 164.930 167.26UNpPu AmCmBkCfEs Fm93 94 95 96 97 98 99 100uraniumplutoniumamericium curium berkelium californium einsteinium fermium238.0289 237.0482 244.0642 243.0614 247.0703 247.0743 251.0796 252.0829 257.0951neptuniumprotactiniumTm Yb69