Kr7. wd /J-t- To pick up your graded exam from a box outside 5100A Pacific Hall sign here:

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1 wd /J-t- To pick up your graded exam from a box outside 5100A Pacific Hall sign here: Kr7 chemtsrry 140A FTNAL EXAM 1v & s 6" Eo1 DEC 8,2011 NAME (please print) SIGNATURE FIBST LAST ID NUMBER LAST NAME OF PERSON SEATED ON YOUR RIGHT: LAST NAME OF PERSON SEATED ON YOUR LEFT: DO NOT OPEN THE EXAM UNTIL YOU ARE TOLD TO DO SO Please sign your name on the top of each page. Please check to see that you have 9 pages (including this one). The one blank page may be used for scratch work, but oo Nor use the scratch page for answers and do not detach the scratch page. Answer in the space provided. Do not write answers on the back of a page. Question Points Score Total 200 He LiBe B C N O F NC NaMg AISiP S CIAr K Ca Sc Ti V Cr MN FE CO Ni CU ZN GA GC AS SE BT KT Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe Cs Ba La Hf Ta W Re Os Ir Pt Au Hg TI Pb Bi Po At Rn

2 u/rf, ""E 1-i. T/T7ry qffi#t,ryfrn (35 pts) For each of the following one-step transformation show the movement of electrons by using the standard curved arrow notation, Show all formal charges for each structure to the left and to the right of the reaction arrows. In the box below each reaction arrow indicate which of the following reaction types includes that mechanistic step: SNl, SN2, El,E2 or "other". a). \---1,/-\ HH OM HOEt b) g -i., ll -b-oacr-oh t\o Hzo ".. ME-C:O *rp fro!cr- o w Mq qyt\ Md \/ '"\,rt" d) E [/l g ",.,... r^ - /"-"\H n...c H3 +1v e) Br-t!.rBr \--x;--l - a;d $Br e1,rb' P' I 2

3 LLf tt'e 1-ii. (35 pts) In the boxes provided, draw the structure of the starting material needed for each of the following transformations. In all cases the starting materials must be optically pure compounds' Be sure to clearly show stereochemistry. For questions "a" and "d": in the box provided give the of the -ryurfig\ation -cgrf+glq indicated stereocenter. /-- ) a) lryy,#- /l*o O 1 tf 6+44tt b) 1) Li B o oh \t r 2) H2O, H* EtM a mixture of two diastereomers ^ : rl 1) TsCl, py N3 I 2) NaN3 a single enantiomer $/q { HO O d) e) G,'ftn -db) 0. hlit \) (h oh, 6t t H+, NaOtBu tbuoh a racemic mixture r->h E;l /t7- \ l--: \ Fo i a singlenantiomer e,11r,, etlart,d,

4 \l/[t t T. 2-i. (60 pts) For each of the reactions shown below, draw the structure of the major product(s). Where appropriate, write "No Reaction". Assume all chiral starting materials are optically pure. Show stereochemistry lvhere appropriate. If the major product is formed as a mixture of diastereomers then place an " x" in the small circte. If the major product is formed as a single etutntiomer, place an " x" in the small box. If the major product is formed as a racemic mixture place an "x" in the small triangle. lrn tn<il a) r FdA ltr1-'r< rv/.t? rt,{,,9o6o, t "f.) a"*. SOCI2, py b),oftt' + Na OTA HBr 0"c d) *"'-...f PrA t Et.., fvle - oap,. 2HBr e< tt, I /, n*+ o, li or o\ I +ll cl''"\-/ IA N'J2,tltU ce'{j A,b OFA

5 q/ I+ ( t4. 2-i (cont). (If the major product is formed as a mixture of diastereomers then place an "x" in the small circle. If the major product is formed as a sinple enantiomer, place an " x" in the small box. If the major product is formed as a racemic mixture place an "x" in the small triangle.) s) NaO 1) Li 2) Br *rrd J 4 l\ is no "x" to mark for this one) h) <e+{ 1) PCC, 2) EtLi 3) H2O otr *"\/" AB, Na Hzo OTA A LiAlD4_ : O OFA

6 i,,rh rtre 3-i. ftntr (I 5 pts) Provide an efficient synthetic route to I starting from II. show the product formed in each reaction that you employ. - \-^--JLff o gl{u -X' ficfrtju;'-^-f^/,#*.45 v * fcc ct&-,tttrt't r fa) You need not show mechanisms but do \ G,D K *< dlkh, -rd r)h;^ft& '-,=.-J\4t 3-ii. (15 pts) Provide an fficient synthetic route to III starting from IV. show the product formed in each reaction that you employ. --o L- -' CK\-- III r\'t r Li t- r) kd o- IV ff* You need not show mechanisms but do ON Wttt"4 ) {i', a rpn * ftlott

7 a,ff t tt (25 pts) In the boxes provided, give the reagent(s) need for each of the following transformations. More than one set of reagents may be necessary for a given transformation. T,T- a) 3S^' )QE.lg t a) onl rlo f w ; : b) Y I %,<^3 tooy t-ill -'= o4 th tl t\ T?L( ' ff - {2," \---\-/ l i CN d) J* ) rfr' 4A+e 4 44,t \ Fo' e) "\--Bt q \--oh

8 ,/-tt f 7 4-ii. (15 pts) Give a detailed mechanism (curved arrow notation) for conversion of V to VI. ryet VVI T ch3no2 ---_-> A tt\.e K * *"al /Y,,,Et \_/ Br rsap )( y'*f #4,,4 tr \ L) / r tvr"''(tt 'noj L, v&aetvsre.) ;1ffir/-,t4nrg (r rn\ rpd HeA avavtd, -Ar(-uutl