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    10 views15 pages

    2011 Final Answer Key 2chqcg3

    Uploaded by

    Bree Elaine

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    © All Rights Reserved
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    Initials: 1 \dvanced Organic Chemistry 2011 ~- Final Exam Please answer the following questions clearly and concisely. In general, use pictures and less than 10 words in your answers. Write your answers in the space provided Write your initials on each page you want graded. There are 17 total pages to this exam. The last 2 pages were intentionally left blank and may be used for scratch paper. Please be sure your copy has 17 pages before you begin. Molecular models are allowed. Calculators are unnecessary and prohibited. Potentially Useful Information kg/h = 2.083 x 10° s"K™ x =1 (kappa) R= 1.98 cal/imol-K log (X") = n log X log (X-Y) Problem Points 1 AS 2 18 3 i) 4 ne 5 24 6 Ne 7 AS TOTAL /100 Initials: 2 Bprs ea 1. (15 points) Predict the major product of the following reactions. Clearly indicate the stereochemistry where appropriate. MeO, cN @ ae + | 2 I (b) © (@) © Initials: 3 2. (8 points) Which configuration of the imidate will be favored: E or Z? Please briefly, but clearly, rationalize your prediction. eaaaaie H,CO~ ~CH, \ Hsco7 SoH (Byimidate (rimidate ye 7 > / H %, vf ( / ‘ € tho ‘ 2A a AY RK Wetter Kabiliapiton Riso = AL , - ee OT thy 6-0 s sguere diy u " aa Initials: 4 3. (10 points) Please draw a reasonable mechanism for the following transformation (Grigg, R.; Redpath, J.; Sridharan, V.; Wilson, D. Tetrahedron Lett. 1994, 35, 7661). 10 mol % Pd(OAc)g 20 mol% PPh 1 BusSn % po Me ELNCI O FARR ny + PR: palond + ha —> PR)n 3 76% if ec 20 15 in . Te = earains eaten &3 alee CX me Q aa Me -L1 ~—_Lne i] be c=0 -L \ Ln Trp CO Initials: 5 APIS cach. 4. (12 points) Jacobsen and Uyeda published the following enantioselective, guanidinium-catalyzed reaction (Uyeda, Jacobsen, E. N. J. Am. Chem. Soc. 2011, 133, 5062). . whee ama fr oer IO om en Tahal woh LE OL a | oe Tae sample: eae OU aE amaiR=Pn (a) What type of rearrangement is this? Please characterize it as is appropriate for this reaction class. [3,31- siqmatvopic rearrangeme nt (Ctacsen) = (b) What types of interactions are shown between the guanidinium catalyst and the substrate in the transition state structure above? Hydrogen bonding (c) The authors found that the enantioselectivity of the reaction depended on substituents on the catalyst, as shown in the table below. Please suggest a rationale for these results. catalyst catalyst substituent exptler" expt! AG" (kcal/mol)? : 6334005 14s-bo01 met ore or Os" eo %» so1t020 129002 * 2eikoor 059740002 sed “ pentsuore 380:+001 0830-10001 a? oi cation intouctton lctween Pr of catalyst + devetoein aM sulsrvate Move ehectven ch ¥\ > better tedonors—> higher er. T-Systems Initials: 6 oS ee 1s ach 5. (24 points) Fagnou et al. developed an interesting arylation using pyridine N-oxides via C-H activation and undertook detailed mechanistic experiments to gain insight into how this reaction works (Sun, H.-Y.; Gorelsky, S. |.; Stuart, D. R.; Campeau, L.-C.; Fagnou, K. J. Org. Chem. 2010, 75, 8180). 5 mol % Pa(OAc)y Br _1Smol% PEELS HEF . + i G00, Phe e 110°C, 16h 3 Noxide Aer N A (a) Below was the generally accepted mechanism for this transformation before Fagnou's studies. Write a rate law for this catalytic cycle in “one plus” format, assuming Step 2 is rate-limiting and subsequent steps to regenerate Pd(PRs) are fast and irreversible. You may also assume that steps prior to the rate-limiting step are rapid and reversible compared with the rate-limiting step. For now, assume that Pd(PRs)2 may be a catalytically relevant species. Pd(PRa)o ka Why ~ + Pi | - PRs a2 Pa(PRe) ne Ky at-Br (A) o Pp te step 1 (rspypgr™ (Rap )Pd~ SW Initials: (5 — continued) () Fagnou measured the relative rates of the reactions of N and ds-N and found kx/ko = 3.3. Is this consistent with Step 2 as the rate-limiting step? Please briefly explain. Yes : Prema, Ceavoge- 4 HOA on ALo 2 ie HONS oD o ie " dN LIE Cowsisdert w] rake Limding cok bond ak as? (c) What do the following graphs tell you? Please note that these are log plots of the initial rate dependence on the concentrations of the various reactants. 350 400 080.970 080-050 Zero ordu in Cal y = 0.0430. 11x - 2.6820.06 \e 040-030 020 019 000 tootaren Initials: (6c — continued) 200 250 300 280 y= 1.1620.12x-2.4040.07 R?= 097 2 100-080 = 060-0020 0.00 logIN-Oxide) 2.00) 220 240 togiRatey 280 200 2.00 + y = -0.02#0.05x - 2.3740.07 160 150 140-430-420 440-400 -0.90 loottigana} First order in CNA x \ Zevo order ia CPRa) *\ Initials: 9 (5~still going) , 2 @ Please simplify your proposed “one-plus’ rate law in Part A to show that it is consistent with the data in Part B. Only Catalyst veshy states oxidative addn pat. gly CPA LT CAIENT/p-1 Yuk CPD GOW YE yer £Pd CH] FOR 7 y tad, Meicbes Ver euER + Aicchs A i Kr % 1 7, 1St order in N- No rate dependence on CA or DORs) it i \ (e) Based on the data, what is the catalyst resting state? (No explanation is necessary.) x2 (esp ac oe) Sr er S a» ss Initials: 10 % 2” (5 — almost there) (f) Fagnou also determined the initial rate dependence on the concentration of Pd(PRs)s (shown in the following plot). What does this data tell you? Is it consistent with the proposed mechanism? If not, please provide a revised catalytic cycle that accounts for all data. 100 180 200 x \ ju] ao Slept = 0-8 i * 300 walk oven in (Pd, = 0.56#0.05x - 1.3040.09 “8 e088 MT Inconsistent, palPRS 5 +6t3 |] —PRe ca * We = 2 wap, = we a Nr cia wy mame 3? ae Wt (mmo quve olumer ) Initials: 1" (5 last bit) (g) Fagnou went on to study the specifics of the C-H activation step (Step 2). Using computational and stoichiometric studies, he found that the bromide exchanges for acetate (OAc), and the acetate participates in the C-H activation via the transition state shown below. The numbers shown represent the computationally predicted energy barriers for C-H activation at each of the 3 sites of the aromatic ring. Based on these energies, predict the ratio of the three regioisomers you expect from this reaction + rr 3 bet * as9 BOGE, pg = eer OE Ces ~ 383 Ortho C-+H activation: AG* = 34.1 kcal/mol oe f oO Meta C-H activation: AG*= 36.3 kcalimol fy oO ie Para C-H activation: AG* = 35.9 kcallmol PK bes o Ls + BIG om /er kp. ent /er 2 e , carured) [2 Aue (400k ‘ne nt14,.) |rscanpet noo) KP... Bv0rrHeetd/(2 Azneh DN (0200 %Awet) /(2 xa fowiB)(KOO ie \ Va. xe” x 80 bax ( . £ (h) What does the following data tell you? \ ot e- Mm x Br a

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