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cHEMtsrRy 140A NAME (please print)

Kr7

FTNAL EXAM 1v & s 6" Eo1DEC 8,201 1

FIBST LAST

SIGNATURE

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 pagemay be used for scratch work, but oo Nor use the scratch page for answers and donot detach the scratch page. Answer in the space provided. Do not write answerson the back of a page.

Question Points Score

1. 702. 603. 304. 40

Total 200

HeLiBe B C N O F NC

NaMg AISiP S CIArK 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

1-i.

u/rf , ""E

NAME:

(35 pts) For each of the following one-step transformations show the movement of electrons by using thestandard curved arrow notation, Show all formal charges for each structure to the left and to the right of thereaction arrows. In the box below each reaction arrow indicate which of the following reaction types includesthat mechanistic step: SNl, SN2, El,E2 or "other".

T/T7ryqffi#T,ryfrn

€OM

a)

Me. Me\---1, / - \

HHHOEt

b)Meg

Me-i. , l l-b-oAcr-oHt\o

Hzo

Me"..

ME-C:O

*rp

f ro!Cr-OH

o

c)

d)

Me

Me

Me

Me

Mq '"\,rt"qYt\Md

\ /w

E

[/l g ",.,..... r^ - n......C H3

Me/"-"\H

+1v

e1

"@e)

,rB'P'I

OH

Br-t

! . rBr\--x;--l

H/@'s,.-

2

a;d $Br

1-ii.

LLf tT'e

NAME:

(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 -ryurfig\ation

of theshow stereochemistry. For questions "a" and "d": in the box provided give the -cgrf+glq

indicated stereocenter. /-- )a) lryY,#-/l*o O

1 t f6+44tt

1) MeLi B oMe oH\ t rEtM

a mixture of twodiastereomers

b)

c)

d)

2) H2O, H*

1) TsCl, py N3

I

a single enantiomer2) NaN3

HOMe

H+, MeOH

a racemic mixture

OH

r->H E;l/ t7-\ l - - :

\------.-FoMeiMe

a single enantiomer

te)

NaOtBu-----..---------

tBuoH

^ r l

:

{

$/q

G,'ftn-db)

OMe

0 . hlit\)

(h oh,

6t

e,11r,, etlart,d ,

2-i.

\l/[t t T.€

NAME:

(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.

a)

lrn tn<il+----

r FdA ltr1-'r< rv/.t

? rt,{, ,9o6o, t

OH"f

.)

a"*.

SOCI2, py

NaOH+

b)

c)

d)

,oftt'

OH

HBr

OTA

e<tt, I/, n*+ o,

l i or

*"'-....fPrA

t Et. fvle 2HBr

., -oAp,.

0"c

I+ l lcl''"\-/ IA

N'J2

o\

ce'{JA,b

, t l tU OFA

2-i (cont).

q/ I+ ( t4.

NAME:

(If the major product is formed as a mixture of diastereomers then place an "x" in the smallcircle . If the major product is formed as a sinple enantiomer , place an " x" in the small box. If themajor product is formed as a racemic mixture place an "x" in the small triangle.)

NaOMe

MeOH

1) MeLi

2) MeBr

1) PCC ,

2) EtLi

3) H2O

NaOH

LiAlD4_

J

*rrd4

l\

s)

h)

is no "x" to mark for this one)

<e+{

otr

OTA

A

:

OFA

*"\/"

MeAB, Hzo

OMe

You need not show mechanisms but do

G,D\ K *< dlkh,

- rd

r )H;^f t&c)

'-,=.-J\4t

i,,rH rtrE

NAME:

(I 5 pts) Provide an efficient synthetic route to I starting from II.

show the product formed in each reaction that you employ.

-X'\-^--JLff

fcc*

ct&-,tttrt't rfa)

(15 pts) Provide an fficient synthetic route to III starting from IV.

show the product formed in each reaction that you employ.

3-i.

o

- gL{u ficfr-

tJU;'-^-f^/

,#*.45v

--oL- -'

ftNtr

You need not show mechanisms but do3-ii.

CK\--III

r\ ' t r Lit-

r ) |kD

ON

ff*Wttt"4

t l@4 a

rpn *

ftlott

o-IV

)-@-{i',

a)

a,ff t ttNAME:

(25 pts) In the boxes provided, give the reagent(s) need for each of the following transformations. Morethan one set of reagents may be necessary for a given transformation.

)QE.lg t

a) oNl rlof

b) I

Y

t\ T?L( th tl' f f -{2,"

J* ) rfr' 4A+e

4 44,t

"\--Bt \--oH

T,T-3S^'

w;:

OH

\---\-/l

i

CN

c)

d)

e)

\Fo'

%,<^3

tooY t-ilL-'= o4

q

,/-tt f 7€

NAME:

4-ii. (15 pts) Give a detailed mechanism (curved arrow notation) for conversion of V to VI.

ry*"al

BrEt cH3No2

/Y,,,Et- - -_->| |

A \_/

VVI

T rsaPtt\.e K *

)( y'*f

#4,,4 tr \L)

/ r / i .F@o- tvr" ' ' ( tT

'noJ

L, v&Aetvsre.) ;1ffir/-,t4nrg(r rn\

rPDHeA

aVAvtd,|-Ar(-uutl