Professional Documents
Culture Documents
1871 (196S).1
lRcpriated lroo thc tournrl ol the Aqcriceo Cbeoicd Society,91,
lg0g by thc Aoericao Cheoicd Socicty rnd reprintcd by perrnirsioo ol thc copyright ottlc(.
Copyright
SanFilipPo,Jr.,
WilliaryF. Fischer,Jr.,Joseph
GeorgeM. Whitesides,
RobertW. Bashe,ild HerbertO. House
Reactionof Lithium Dialkyl- and Diarylcupratesw'ith
OreanicHalides''
Filippo. Jr.,3
George NI. Whitesides, lVilliam F. Fischer, Jr.,3 Joseph San
Robert W. Bashe, and Herbert O' House
ContributionfromtheDepartmen|ofChemistr-I.'
02 I 39'
MassacltttsettsInstitute of Technolog'" Cambridge' Massachusetts
Receiced Februurv 7, 1969
or- s i u m r e a g e n t sa r e r e l a t i v e l y u n r e a c t i v et o w a r d s i m p l c
A b r o a d l y a p p l i c a b l ep r o c e d u r ef o r c o u p l i n g t h e
ll g a n i c m o i e t y o f a n o r g a n o m e t a l l i cr e a g e n tw i t h e l k y l a n d a r y l h a l i d e s : t h c i r r e a c t i o nw i t h a c t i v a t e dh a -
t h a t o i a n o r - q a n i ch a l i d e w o u l d b e a u s e f u lm e m b e ro f l i d e s a g a i n i e a c l st o n r i x t u r e so f p r o d u c t s . T ' EO r g a n o -
t h e c l a s s o f r e a c t i o n s a v a i l a b l e f o r t h e s y n t h e s i so [ z i n c a n c lo r g a n o a l u m i n u mc o m p o u n d se x h i b i t l o w r e a c -
carbon-carbonc bonds. Un[ortunaiely'the com- t i v i t y t o w a r d, € . 8 . , n - a l k y l h a l i d e s ' A t p r e s e n t ' t h c
(l) s t r u c t u r a lf a c t o r sr e s p o n s i b l ef o r l o w n u c l e o p h i l i c i t yo f
R M + R , X _ > R _ R ,+ V I X
t h e s e o r g a n o m e t a l l i cr e u g e n t st o w a r d c a r b o n a r e n o t
m o n l y e n c o u n t e r e do r g a n o m e t a l l i cd e r i v a t i v e so [ t h e e n t i r e l ye v i d e n t .
ma i n gr oup m et al s a p p e a r to b e u n s i i ti s fa c to r yas rea- I n c o n t r a s t . o r g a n o m e t a l l i cc o m p o u n d s c o n t a i n i n g
g e n t s lor ef f ec t in g th e fo rm a ti o n o f c a rb o n -carbon carbon-copper(l)bonds provide a class of reagents
b o n d s b y n u c l e o p h i l i c d i s p l a c e m e n ta t a c a r b o n - w h o s eu s e i u l n e s isn c o u p l i n g r e a c t i o n sw i t h o r g a n i c h a -
h a l o g e nb o n d . A l t h o u g h o r g a n o l i t h i u m r e a g e n t sa r e l i des has beenampl y demonstrl ted i n certai nspecialized
s t r o n g l y b a s i c ,t h e y a p p e a r t o b e o n l y w e a k l y n u c l e o - ci rcumstances. i trut reacti on of copper(l ) acet ylides
philic ioward carbon: reaction of an organolithium w i t h a c e t y l e n i c , ea r o m a t i c . r 0v i n y l , [ a ' b a n d a c y F r " h a -
i o * p o u n d w i t h a n a l k y l o r a r y l h a l i d ei n h y d r o c a r b o n . , G r i g n a r dR e a c t i o n so f N o r r -
o r..i h. r s olut ions u s u a l l y l e a d sto m i x tu re so f products ( 7 ) N I . S ' K h a r a s c l ra n d O . R e i n m u t h '
I n c ', Nerv York' N' Y" 19)l'
metallic S u b s t i t n c c s , "P r e n t i c e - H a t t ,
d e ri v ed t ' r om c om p e ti n g m e ta l -h a l o g e n e x c h ange.ta C h a p t e r1 6 .
m e t a l a t i o n , si 3 e l i m i n a t i o n ,a n d c o u p l i n g ,w i t h t h e l a s t ( 8 ) N o r m a n t h a s r e p o r t e d t h a t u s e o f h e x a m e t h y l p h o s p h o r a m i d 'ct s
to
r e a c t i o na p p a r e n t l yp r o c e e d i n ga, t l e a s ti n p a r t , t h r o u g h s o i v e n rf o r t h e r e a c t i o no f a l k y l h a l i d e sw i t h G r i g n a r d r e a g e n t sl e a d s
generalin'
s y n t h e t i c a t l yu s c f u I y i e t d so f c o u p l e d p r o d u c t s ; h o w e v e r ' t h e
a complex free-radicalmechanism'6Organomagne- o [ t h i s s o l v c n te f f e c ih a s n o t y e t b e e nd c m o n s t r a t e d : c f ' H ' N o r m a n t '
A n g e wC. h e n t . l n t .E t t E . n g ! . , - 6 , 1 0 ' 1( 16 9 6 7 ) ;J ' F ' N o r m a n t ' B u l l ' S o c
( l ) s u p p o r t e db y c r a n t s c P - 2 0 1 8 a n d G P - i 2 6 6 f l r o m t h c N a t i o n a l
C h i m .F r . , 1 8 8 8( 1 9 6 3 ) .
S c i c n c cF o u n d a t i o n . (1961);
( 9 ) ( a ) G . E g l i n t o na n d W ' N l c C r a c ,A c ! c a nO' r g ' C h e m " 4 ' 2 2 5
( 2 ) S u p p o r t e c bi y R c s c a r c hG r a n t N o . A F O S R - 6 8 ' 1 5 1 8l r o m t h e
S c i e n c e s ,A i r F o r c e O f f i c eo t ' s c i e n t i f i c R e s e a r c h ' ( b ) F . B o h l m a n n , H ' S c h d n o l o s k v ,E ' I n h o f f e n ' a n d G ' G r a u ' C h e n t '
D i i c c t o r a i eo f C h e m i c a t
( 3 ) N a t i o n a l I n s t i t u t e so f H e a l t h P r e t j o c t o r r lF c l l o w , 1 9 6 6 _ 1 9 6 9 . \ir.,91,794 (1961); (c) R. F' Curtis and J' A' Tavlor' Tetrahedrort
G i l m a n , O r g . R e a c t t o n s , 6 , 3 (
3 1 9 9 5 t ) ; D . E . L ett.,29l9(1968).
i , f i n . G . J o n e sa n d H . (1961); ( t t i l f a ) C . E " C a s t r o , E . J ' G ' r u g h a n ,a n d D ' C ' O r v s l e y 'J ' o r z
A p p i c q u i s ta n d D . F . O ' B r i c n , J . A r n e r . C h e n t .S o c . , 8 5 . 7 4 3 ibid"28'
W i n k l e r , i b i d . , E E ,9 U ' 9 6 9 ( 1 9 6 6 ) ' C h e m . , 3 l ,- t 0 7 1( 1 t 6 6 ) ; ( b ) C . E . C a s t r oa n d R ' D ' S t e p h e n s ' ( 1 9 6 - < ) ;
H. L S. Winklcr and H. ( 1 9 6 3 ) :( c ) R . E . D e i s y a n d s . A . K a n d i l , i b i d . , 3 0 . 3 8 5 7
(5) W. l(irmse, " C a r b c n e C h e m i s t r y , " A c a d c m i c P r e s s N
' e w Y o r k ' 2 1 6 3
(d) R. E. Atkinson, R. F. iurtis, and J' A' Taytor'J' Chem'Soc" C"
N.Y.,1964;G.l(iibrich,Angew'Chem'Int.Ed'Engl',6,'ll(1967)'and J' A'
i ; ' s ( t s o z l : ( e ) R . E . A t k i n s o n , R ' F ' C u r t i s ' D ' M ' J o n e s 'a n d
r e f e r e n c e si n e a c h . 718(1967)'
( 1 9 6 7 ) ; H ' R ' W a r d T a y l o r , C h e m . C o m m u n . '
( 6 ) H . R . W a r d , J . A m e r . C h e m 'S o c ' , 8 9 , 5 5 1 7
( t t l t o l J . B u r d o n ,P . L ' C o c ' C . R ' M a r s h ' a n d J ' C ' T a t l o w ' C h e n t '
and'R.G.Lawler,ibi(t.,89,5518(1967);C.G'screttrsandJ'F' V' I'
C o m n t u n . ,r z s s t l 9 6 i l ; ( b ) L . Y u U k h i n , A ' M ' S l a d k o v ' a n d
E a s t h r m ,i b i d . ,8 8 , 5 6 6 8( 1 9 6 6 ) .
l. (CHr}CuLid I 95 Toluene 3
4 75 6 l6
1{
l5 36 AA 48
42 <l 16 70
cHrl-i (0.1) I .l 4
2. (CHr)zCuLid
4 ll 35
l5 25 65
A'l
+z .18 7L
3. (CHrhCuLid LiBr (1.0) I -l -[
l5 29 60
4. (CHrlCuLid L i r( r . 0 ) I <l <l
34 l6
5. (CHr)rCuLid ( r r - C r H g ) r P( 0 . 5 ) I 20 9l
4 l8 92
6. (CHr}CuLi' Lit (0.5)+ I <l <l
( r r - C r H c ) z S( 1 . 0 ) ,1 1
l9
72 JI 37
7. (CHr!CuLii L i r (0 .5 )+ 025 l2 60
L i B r( 1 . 0 ) t2 l: 60
8. (CHr)zCuLid "residue" o I 55 52
2 99 98
9. (CHr)rCuLid c H 3 L i(0 .1 )+ I J 7
"residue" 4 A 80 80
l5 95 95
10. (rr-C.Ho):CuLiP(rr-Buh^ Lir(0.s) 0.7 rl-CrH rC,;H; <l 50
I l. (sec-CrH,r)zCuLiP(rr-Buh^ Lit (0.5) o.7i sec-CrHgCoHs <l 20
12. "(rt-C.Hc):CuLi"i Lir(0.s) 1.0, rt-C.rHgCoH: <l 55
13. "(sec-C1H,,)rCuLi"i L i r( 0 . s ) I .0, sec-CrH,rCoH; <l <t
. Reactionswcre carncd ou! in erhersolutionat 25', with [RrCuLi] = 0.5 11, and [C.Hill - 0.1 I/, unlessotherwiseno(ed. ' Yiclds
were dcterminedby glpc, and sre basedon iodobenzenc. " Oxidationswere carried out by diluting the reaction mixlure to -0.1 M in Cu(l)
d Pteparedby dissolving hal idc-freem€thylcopper(I)
followed by addition ofan excessof moleculff oxygenat -78', unlessnoted olherwise.
in hatide-fiee methytlithium solurion (eq ?). , Preparedby reaction of 2 equiv of melhyllithium wirh I cquiv of (r'-C.H')rslrcul (eq 8)
/ prepar€dby reactionof 2 equiv of alkyllilhium reagentwith a suspensionof I equiv of Cul (eq 6), , "Residue".refersto the materialspres-
I Pr€paredby re-
enr in commircial copper(l) iodide which are insoluble in di-r-butyl sul6de. See the text lbr a disctrssionof this poin!.
I Relction carriedout a( -10'. )THFsolurion-
acrionof 2 equivof aikyllirhium.eagentwirh I equivof lCuP(r-Bu)r(eq 8).
Th e pr es enc e of t he s el i g a n d sa n d th e i r re a c ti o nproducts taken to avoi d contact betw een the reacti on solut ion
during the w o r k - u p o f r e a c t i o n sc a r r i e d o u t o n a s y n - a n d o x y g e n ( f r o m t h e a i r ) i n t h e r e a c t i o n si n v o l v i n g a
t h e t i cs c a l eh a sc o n s i s t e n t l yp r o v e dt o b e a m a j o r i n c o n - n o n o x i d a t i v e w o r k - u p , t h e p o s s i b i l i t yt h a t s o m e p o r -
venience. t i o n o [ t h e t o l u e n e o r l - m e t h y l n a p h t h a l e n feo r m e d i n
L i t h i u m d i a l k y l c u p r a t e sc o n t a i n i n g p r i m a r y a l k y l t h e s e e x p e r i n t e n t sa r o s e f r o m u n i n t e n t i o n a l r e a c t i o n
g r o u p so t h e r t h a n n r e t h y lc a n i n g e n e r a b l e p r e p a r e db y w i t h a n o x i d a n t c a n n o t b e r i g o r o u s l ye , r c l u d e d . T h e
p r o c e d u r e sa n a l o g o u st o t h o s e o f e q 6 , 7 , a n d 8 , a l - i ncreasei n yi el d of unsymmetri caldi mer on o xidat ion
t h o u g h t h e s o l u t i o n so b t a i n e db y t h e p r o c e d u r eo f e q 6 provi des a qual i tati ve measureof the quanti t y of ar yl-
m a y c o n t a i n a l k y l l i t h i u m r e a g e n ti n a p p r e c i a b l e x c e s s metallic reagent presentin the solution. Additional
o f t h e s t o i c h i o m e t r yr e q u i r e d b y t h e f o r m u l a t i o n R : - evi dencefor the presenceof an aryl metal l i c int er m e-
C u L i . G r i g n a r d r e a g e n t sc a n n o t i n g e n e r a l b e s u b - d i a t e i s d i s c u s s e dl a t e r i n t h i s m a n u s c r i p t . S i n c ea n e x -
sti tu t ed f or or gano l i th i u m re a g e n tsi n th e p ro c edureof cessof l i thi um di methyl cupratew as used i n all st udies,
e q 6 . W e hav e on l r' b e e n s u c c e s s fuiln p re p a ri ngw el l - a n d s i n c eo x i d a t i v ec o u p l i n g o f m i x e d l i t h i u m d i o r g a n -
ch ar ac t er iz eds ec - a n d t-a l k y l c o p p e r(l )re a g e n tsby the ocupratesseemsto gi ve approxi matel ystati sticalyields
p ro c edur eof eq 8. T h e p ro c e d u re se x e mp l i fi e dby eq 6 o f s y m m e t r i c a la n d u n s y m m e t r i c a dl i m e r s , r et h e p r o b -
[wi th c opper ( l) br o m i d e ],7 , a n d 8 w e re a l s o s a tisfactory a b i l i t y o f s y m m e t r i c a lc o u p l i n g o f t h e a r y l m o i e t i e so f
f o r p r o d u c i n ge t h e r s o l u t i o n s o f l i t h i u m d i p h e n y l c u - t w o a r y l m e t a l l i cr e a g e n t su n d e r o x i d a t i v ec o n d i t i o n si s
prate. much l ow er than the probabi l i tv of unsymmetr icalcou-
The pr oduc t s of re a c ti o n o f l i th i u m d i me th yl cuprate pling.
w i t h i o d o b e n z e n ea n d w i t h i o d o n a p h t h a l e n ew e r e i n - The data of Tabl e I summari ze observat ionscon-
t e r r e df r o m a c o m p a r i s o no f t h e g l p c t r a c e so f t w o a l i - c e r n i n gt h e r e s p o n s eo f t h e y i e l d o f t o l u e n ei n c o u p l i n g
q u o t s : o n e a l i q u o t w a s h y d r o l y z e dd i r e c t l y ;t h e s e c o n d of l i thi um di methyl cuprate w i th i odobenzene t o i. I
w a s f ir s t ox idiz edu s i n g a n e x c e s so f mo l e c u l a ro xygenor n u m b e r o f t y p e s o f c h a n g e si n r e a c t i o n c o n d i t i o n s .
n i t r o b e n z e n ea. n d t h e n h y d r o l y z e d . U s i n g t h i s a n a - T h e r e a c t i o no I p u r e l i t h i u m d i m e t h y l c u p r a t w e ith iodo-
l y t i c a l p r o c e d u r et,h c y i e l d o f t o l u e n eo r l - m e t h y l n a p h - benzenei n hal i de-fi reeether appearsto be com plet e in
t h a l e n e o b t a i n e d f o l l o w i n g t h e n o r t o x i d a t i v ew o r k - u p 2 4 h r o r l e s sa t 2 5 o . T h e y i e l d o f t o l u e n ei n t h e n o n -
p r e s u m a b l yp r o v i d e sa m e a s u r eo f c o u p l i n gt a k i n g p l a c e oxi dati ve w ork-up, and the i ncreasei n yi el d o f t oluene
b y s onr ec om binati o n o f re a c ti o n sre p re s e n te db y eq 2, o n o x i d a t i o n .d e m o n s t r a t et h a t t h e p r o d u c t so f c a r b o n -
3 , a n d - 1 . A l t h o u g h i t n u m b e r o f p r e c a u t i o n sw e r e carbon bond formati on and metal -hal ogen exchange
f o r m a t c o m p a r a b l er a t e s . S i m i l a r d a t a f o r r e a c t i o n s m e t h y l l i t h i u mw i t h a r y l i o d i d e si n t h e a b s e n c eo f c o p p e r
w i t h l - i o d o n a p h t h a l e na e r e p r e s e n t e di n T a b l e I I ; i n s a l t so f t e n g i v e sy i e l d so f c o u p l e dp r o d u c t sc o m p a r a b l c
t h i s c a s ec o n s u m p t i o nb y t h e a r y l i o d i d e i s c o m p l e t ei n o r s u p e r i o r r o t h o s e o b t a i n e du s i n g l i t h i u m d i m e t h y , l -
less than 8 hr. The addition of lithium bromide, cuprate. However, comparison of entries I and l
lithium iodide, or di-n-butyl sulfide to solutions ot of rabl e I establ i shes thar the presenceof me t hyilit hiur '
lithiumdimethylcuprare ( t ) p r e p a r e df r o m p u r e m e t h y l - i n excessof the stoi chi omerryrequi red by the f or m ula-
c o p p e rh a s r e l a t i v e l yl i t t l e e f r e c to n t h e r a t e e i t h e ro f t h e t i o n " ( C H r ) , C u L i " d o e s n o r a p p r e c i a b l ye n h a n c e t h e
m e t a l - h a l o g e ne , \ c h a n g er e a c t i o n o r o f t h e c o u p l i n g r e a c t i v i r yo f t h e c o p p e r a r e c o m p l e x i n t h e c o u p l i n g
reacrion. Addition of I equiv of tri-n-burylphosphine reaction.
t o a r e a c t i n gs o l u t i o n o f l i t h i u n r d i m e t h y l c u p r a t ea n d A possi bl ecl ue to the di fferencei n reactivit y of pur c
i odobenz enehas tw o e ffe c ts : i t i n c re a s e sthe rate of lithium dimethylcuprare a n d m a t e r i a lp r e p a r e dd i r e c t l y
m et al- halogene ,rc h a n g ea s j u d g e d b y th e y i e l d of tol - from methyllithium and commercial copper iodidc
u e n eo b t a i n e do n o x i d a t i o n ,a n c li t i n c r e a s etsh e r a t e o f a p p e a r si n c o m p a r i s o no f e n t r i e s2 , 7 , 8 , a n d 9 o f T a b l c
t o l u e n ef o r m a t i o n p r i o r t o o x i d a t i o n . I. The ether-soluble c o m p l e xo f d i - n - b u t y ls u l f i d ea n c l
C o m p a r i s o no f e n t r i e s l , 3 , 4 . a n d 7 o f T a b l e I a n d c o p p e r ( l )i o d i d e u s e di n t h e p r e p a r a t i o no f p u r e m e t h y l -
s i n r i l a rd a t a i n T a b l e I I e s t a b l i s h etsh a t t h e r e a c t i o nb e - c o p p e r ( t ) ( e q 7 ) i s o b t a i n e d b y d i s s o l v i n gc o p p e r ( l)
tween aryl iodidesand pure lithium dimethylcuprate. iodide in the sulfide. Commercial "copper iodide"
p r e p a r e df r o m m e t h y l l i t h i u m a n d m e t h y l c o p p e r ( l ) i, s ordi nari l y contai nsapproxi matel y5 ft i mpur it ieswhich
a p p r e c i a b l ys l o w e r t h a n t h a t w i r h l i t h i u m d i m e t h y l - are insoluble in di-n-butyl sulfide. Entries 8 and 9
cu pr at e pr epar e d b y re a c ti o n o f m e th y l l i t hi um and summari zeexperi mentsi n w hi ch thesedi -n-but yl sulf ide
c o p p e r ( l )i o d i d e : t h e l a t t e r r e a c t i o na p p e a r st o b e c o m - i nsol ubl e resi duesw ere col l ectedand added t o copper
p l e t e i n l 5 - 3 0 m i n . w h i l e t h e f o r m e r p r o c e s sr e q u i r e s ate compl exespreparedfrom pure methyl co pper . Sur -
8 -2- l hr . F ur t he r, a l th o u g h th e y i e l d o f to l uene ob- pri si ngl y, i t appearsthat addi ti on of these r esiduest t r
tained on oxidation of the latter reactionmixture is the organocoppersol uti onssi gni fi cantl yenh ancest heir
c o m p a r a b l et o t h a t o b t a i n e d o n o x i d a t i o n o [ r e a c t i o n reacti vi ty i n the nono,ri dati vecoupl i ng react ion. Wor k
mixturesincorporatingpure lithium dimethylcuprate, i n progress i s desi gnedto expl ore the si gnif icanceot -
t h e y i e l d o f t o l u e n ep r o d u c e di n t h e d i r e c tc o u p l i n gr e a c - t h e s eo b s e r v a t i o n sa.n d a n y d i s c u s s i o n of themechanism
ti o n is s ignif ic an tl yl o w e r. T h u s . i t a p p e a rsth at metal - by w hi ch the di -n-butyl sul fi dei nsol ubl eresiduesm ighr
h alogenex c hang ei s s i g n i fi c a n tl ,vmo re ra p i d usi ng the i n f l u e n c et h e c o u r s eo f t h e c o u p l i n g r e a c t i o ni s c l e a r l y '
re a gent pr epar e d b y re a c ti o n o f m e th y l l i th i um and specul ati on. N onethel ess.these resul ts ra ise t he in-
c o p p e r ( l )i o d i d e r h a n u s i n g p u r e l i t h i u m d i m e t h y l c u - triguing possibility that metals,other than copper,
prate. p r e s e n ti n t h e r e s i d u e sm a y b e c a p a b l eo f c a t a l y z i n gt h c
The r eas on f or th e o b s e rv e dd i ffe re n c e si n reacti vi ty c o u p l i n gr e a c t i o n . : {
o f t he or ganom e ta l l i cre a g e n tsp re p a re d b y th e proce-
d u r es r epr es ent e db y e q 6 a n d 7 i s n o t p re s entl ycl ear. yielded 86% l-methylnaphthalene. Consequently, the direcr reection
with methyllithium appears to bc the merhod of choice for synthcrrc
Methyllithium itself reacts readily with iodobenzene mcthylation reactions involving aryl iodides when other function.rl
to y ield t oluene .!3 In fa c t, th e d i re c t re acti on of groups in the organic iodide are compatibte with this organometallic
reagent. Comparison of these yieids and reacrion times with those in
( 2 3 ) ( a ) H . G i l m a n a n d F . W . M o o r e , J . A m e r . C h e m .S o c . ,6 2 , l g 4 j Table I provides chemical evidence that solutions of lithium dimethl,l-
( 1 9 4 0 ) ; ( b ) W . L a n g h a m ,R . Q . B r e w s r e ra, n c lH . G i l m a n , i b i d . , 6 3 , S 4 S cuprate do not contain appreciable concentrations of free methyllithium.
( l 9 , l l ) . I n o u r h a n d s , r e a c r i o n o f I e q u i v o f m e t h y l l i r h i u mw i t h I (24) Nore Apoeo rx PRoor. Semiquantitative flame spectropho-
e q u i v o f i o d o b e n z e n ei n e t h c r y i e l d e d9 l f t o l u e n ei n 3 0 m i n a t r o o m tometric anal-vsis of a representative sample of the di-n-butyl sulfidc
tempcraturc. Under similar reaction conditions, l-iodonaphthalcne insoluble "residue" in commercial copper(I) iodide has established thar
l,l,'lritesides,
et al. I Litltium Diulk-t'l-und DiarT'lcuprctte
Reuctions
876
I. 2.; CuBr.T IIF. - ;3.
sec-C1H,Li* 4CnH;Li ec-CrHnCrH; s o i u t i o n s : i n m o s t o f t h e s e r e a c t i o n sw e h a v e e x -
G, -;30 amined.the yields of couplcd product obtained after
(76/"1
l . 2 . 5 C t r l l r ,T I I I ' . - 7go e i t h e r o x i d a t i o n o r h y d r o l y s i so f t h e r e a c t i o nm i x t u r c s
t-C.{HJLi * 4CrHrLr --+ l-C{HcCeHi a r e v e r y s i m i l a r . S i n c e r h e o . r i d a t i o nq f l i t h i u m d i -
2. O:, - 78"
(737'1 a l k y l c u p r a t e sg i v e s g o o d y i e l d s o f d i m e r i c p r o d u c t s . r l
R e a c t i o no f L i t h i u m D i p h e n y l c u p r a t e with Aryl and t h i s o b s e r v a t i o ni n d i c a t e st h a t t h e s er e a c t i o ns o l u t i o n s
Viny'l Halides. The reacrion of lithium diphenyl- d i d n o t c o n t a i n s i g n i f i c a n tc o n c e n t r a t i o n so f o r g a n o -
c u p r a t ew i t h l - i b d o n a p h t h a l e n(eT a b l e t I I ) a p p e a r st o m e t a l l i c c o m p o u n d s c o r r e s p o n d i n gt o t h e s t a r t i n g o r -
f o l l o w a p p r o x i m a t e l yt h e s a m e p a t t e r n t h a t a p p e a r e d g a n i c h a l i d e s .a r t h e p o i n t a t w h i c h t h e o x i d a n t w a s
i n r e a c t i o n so f t h e m e t h y l r e a g e n tI w i t h l - i o d o n a p h - added. Although this fact does not by itself exclude
t h a l e n ea n d i o d o b e n z e n e . T h e o p e r a t i o n o f m e t a l - t h e p r o d u c t s o f m e t a l - h a l o g e ne x c h a n g ea s t r a n s i t o r l .
h a l o g e n i n t e r c h a n g ei n t h i s r e a c t i o n s y s t e mi s u n a m - i n t e r m e d i a t e si n t h e c o u p l i n g r e a c t i o n , t h e o b s e r r . e j
b i g u o u s l . cv o n f i r m e d b y t h e o b s e r v a t i o nt h a t h y d r o r y s i s s t e r e o c h e m i s t roy I t h e r e a c r i o no f l i t h i u m d i p h e n , v - l c u -
o f a r e a c t i o na l i q u o t w i t h D : O a f t e r t h e m e t a l - h o l o g . n prate w i th (-)-(n)-2-bromoburane (ui de i nf r a) r encler s
e x c h a n g eh a s t a k e n p l a c e l e a d s t o n a p h t h a l e n eh a v i n g t h i s r e a c t i o nc o u r s eu n l i k e l y . T h i r d , c o u p l i n g si n v o l v -
i s o t o p i cc o m p o s i t i o n 8 0 7 4 d r , 2 0 % d o , & n d b y t h e s i - i n g a l k y l h a l i d e sa r e s i g n i f i c a n r l yi m p r o v e d b y u s i n g a
nruitaneoua sppearance o f i o d o b e n z e naen d n a p h t h a r e n e p o l a r s o l v e n t s u c h a s t e t r a h y d r o f u r a na s t h e r e a c t l o n
i n a o p r o r i m a t e l y e q u a l y i e l d s f r o m h y d r o l y s i so f a l i - medium.
q u o t s t a k e n e a r l y i n t h e r e a c t i o n . M e t a l - h a l o g e ne x - S e v e r a ls p e c i f i cp o i n t s c o n c e r n i n gt h e d a t a i n T a b l e
c h : r n g ei s c o m p l e t ei n a p p r o x i m a t e l y4 h r a t r o o m t e m - I V d e s e r v eb r i e f c o m n r e n t . F i r s t , l i t h i u m d i m e t h v l c u -
p c r r t u r e : t h e c o u p l i n g r e a c t i o n ,w h i c h m a y r e f l e c e p r a t e ( 1 ) p r e p a r e df r o n t m e r h y l l i r h i u ma n d c o p p e r ( l )
t ither
d i r e c r r c a c r i o n o I l i t h i u m p h e n y l l(- n a p h t h y l ) c u p r a t e o d i d e a p p e a r st o h a v ' et h e s a m e r e a c t i v i t yt o w a r d a l k , , l
i
* ' i t h t h e i o d o b e n z e n e f o r m e d i n t h e e x c h a n g e ,o r h a l i d e sa s d o e s p u r e l . S i n c e t h e d i f f e r e n c eb e t w , e e n
thr'rntad l e c o m p o s i t i o no l a l - n a p h t h y l c o p p eorr g a n o - t h e r e a c t i v i t y o f t h e s e r e a g e n t st o w a r d a r y l h a l i d e s
n l e t a l l i cr e a g e n ti n t h e p r e s e n c e o f a p h e n y l c o p p ecr o m - s e e n r e dt o b e r e l e t e dt o a d i f l e r e n c ei n t h e i r a c t i v i t l , i n
p o u n d . c o n t i n u e s n t o r e s l o w l y . R e g a r d l e s so f t h e m e t a l - h a l o g e ne x c h a n g e t. h e i r s i m i l a r i t yi n a r e a c t r o n
n r e c h a n i s nt r f t h e t h e r m a lc o u p l i n gr e a c t i o n o. x i d a t i o n s y s t e m i n w h i c h m e t a l - h a l o g e ne x c h a n g ea p p a r e n r l v
c r it h e m i x t u r e o t ' o r g u n o n r e t a l l irce r g e n t so b t a i n e da f t e r d o e s n o t t a k e p l a c e i s n o t s u r p r i s i n g . S e c o n d ,i t a p -
t h e i n i r i a lm e t a l - h a l o g e ne x c h a n g er c u c t i o ni s c o m p l e t e p e c r s t h e t i t m a v b e p o s s i b l ei n c e r t a i n c o u p l i n g r e i t c -
r c s u l t si n e f t i c i e n ct o n v ' e r s i o o n f l - n a p h t h y l m e t asl p e c i e s t i o n s t o u s c a m i x t u r e o f t t r g a n o l i t h i u mr e a g e n t a n t i
p r c s e n t i n s o l u t i o n t o l - p h e n y l n a p h t h y l e n eO . nce c a t a l . r ' t i cq u a n t i t i e s o f c o p p c r ( l ) i t t n i n p l a c e o f p r c -
a g l i n . n i t r o b e n z c n ea p p e a r st o p r o d u c e t h e h i g h e s t f o r m e d d i i t l k y l c u p r a t e st o e f l ' c . ctth e c o u p l i n g r e a c t i o n .
v i e l d s o f I - p h e n y l n a p h t h a l e nien t h e o x i d a t i v ec o u - a l b e i t a t a p p r e c i a b l ed e t r i r n c n r t o r e a c t i o n r a t e a n t i
p l i n g : o r i d a t i o nw i t h o x y g e ne i t h e rr r r0 o o r a t - 7 8 o , p r o d u c t y i c l d . T h e r e a c r i o no f t h r e e f o l dm o l a r e x c c s s
n r t r o m e t h a n eo, r c o p p e r ( l l ) c h l o r i d eg i v e sa p p r e c i a b l y o f I w i t h r r - o c t y li o d i d e t t t v i c l d / r - n o n a n et a k e s p l a c e
l c r w €yf i e l d s . q u a n t i t a t i v e l iyn l e s st h a n 3 h r . R e a c t i o no f a s i m i l a r
S i m i l a r l y ,r e a c t i o no f a n e x c e s so f l i t h i u m d i p h e n y l - q u a n t i t yo I m e t h y l l i t h i u mw i t h r r - o c t y il o d i d e f o r l 2 h r
c u D r a t ew i t h 1 , 8 - d i i o d o n a p h t h a l einner e f l u x i n gd i e t h y l yields only 6% n-nonane. Howcver, addition oi 5
e t h e r s o l u t i o n f o r e x t e n d e dp e r i o d so f t i m e a p p e a r st o m o l I c o p p e r i o d i d e ( b a s e do n l - o c r y l i o d i d e ) t o r h e
r c s u l t i n a p p r o x i n r a t c l y 5 0 , | o c o n v e r s i o no f t h e a r y l m e t h y l l i t h i u n r e s u l t si n a 6 l ' ' l y i e l d o I r r - n o n a n ei n l ]
i o d i d e t o l - p h e n y l - 8 - c o p p e r ( l ) n a p h t h a l eansej.u d g e d h r . T h i r d . l i t h i u m d i - i r - b u r y ' l c u p r ar e t ea c t sw i t h a l n l o s r
b . r t h e d i f f e r e n c ei n y i e l d o f l - p h e n y l -a n d 1 . 8 - d i p h e n y l - e q u a l i a c i l i t y w i t h r r - p e n r y li o d i d e . b r o m i d e , c h l o r i d c .
naphthalene b e f o r ea n d a f t e r o x i d a t i o n . a n d t o s y l a t et o y i e l d / r - n o n a n e p. r o c i d e dt h a t t e t r a h v -
R e a c t i o n o f l i t h i u m d i p h e n y l c u p r a t cw i t h c , . r - o r d r o f u r a n i s u s e da s s o l v e n t . T h e u s eo f d i e t h y l e t h e r a s
tra t t . s ' $- br om osty re nre e s u l tsi n h i g h c o n v e rs ionsto crs- s o l v e n tr e s u l t si n l o w e r y i e l d so f c o u p l e d p r o d u c t sw i t h
a n d t r c n . r - s t i l b e n e sr e, s p e c t i v e l y ;o x i d a t i o n i s n o t r e - n - p e n t yb l r o m i d ea n d c h l o r i d e ; t h eu s eo f p e n t a n ea s s o l -
q u i r e d i n t h i s r e a c r i o ns y s r e mt o o b t a i n h i g h y i e l d s o f v e n t a p p e a r st o c o m p l e r e l yi n h i b i t t h e d i r e c t c o u p l i n g
c o u p l e dp r o d u c t s . L e s st h a n 2 \ o f t h e s t i l b e n ei s o m e r r e a c t i o n . T h e s eo b s e r v a t i o n sa r e i n q u a l i t a t i v ea c c o r c i
h a v ' i n gi n v e r t e dc o n f i g u r a t i o na r o u n d t h e d o u b l e b o n d w i t h t h e p r o p o s i t i o nt h a t t h e r e s p o n s eo f t h e c o u p l i n g
i s t o r m e d i n e a c h c a s e . F o r r e a s o n sd i s c u s s e dp r e - r e a c t i o n st o c h a n g e si n s o l v e n t a n d l e a v i n g g r o u p a r e
v i o u s l y 2 tsh e o b s e r v a t i o n o f r e t e n t i o n o f s t e r e o c h e m - h o s e e x p e c t e df o r a n S v 2 r e a c t i o n . F o u r t h , a l t h o u g h
t
r s t r y i n t h e s ec o u p l i n g r e a c t i o n ss t r o n g l ya r g u e sa g a i n s t 2 - b r o m o b u t a n ec o u p l e s i n h i g h y i e l d w i t h l i t h i u m d i -
f r e ed - s t y r v lr a d i c a l sa s r e a c t i o ni n t e r m e c i i a t e s . p h e n y l c u p r a t et h. e y i e l d so f c o u p l e d p r o d u c t so b t a i n e d
Reac t ionof Lith i u m D i a l k l ' l - a n d D i a ryl c u pratesw i th o n r e a c t i o no f s e c o n d a r ya l k y ' l h a l i d e sw i t h l i t h i u m c i i -
A l k l ' l H a l i d e s . T h e r e a c r i o no f t y p i c a l l i t h i u m d i o r - a l k v l c u p r a t e sa r e m u c h l o w e r t h a n t h o s eo b t a i n e dw ' i t t r
g a n o c u p r a t e sw i t h a t k y l h a l i d e s( T a b l e I V ) d i f f e r s i n p rimarv halides. The yieldsof coupled productsob-
s e v e r a li m p o r t a n t p r a c t i c a l a s p e c t sf r o m t h e r e a c t i o n s t a i n e d u s i n g t - a l k y l h a l i d e s a r e s o l o w t h a t t h e r c -
w i t h a r , v l h a l i d e s d i s c u s s e dp r e v i o u s l y . F i r s t . t h e s e a c t i o n a p p e a r st o b e o f n o p r a c t i c a l u t i l i t y . I n c o n -
c o u p l i n g r e o c t i o n s u s u a l l v p r o c e e d m ( ) r e r a p i c l t ya n d t r a s t .l i t h i u m d i - . s e c - a l k yal -n d d i - r - a l k y l ( t r i - n - b u t y l p h o s -
i n h i g h e r y i e l d t h a n d o t h e c o r r e s p o n d i n gc o u p l i n g st o p h i n e ) c u p r a t e sg: 0i v eg o o d y i ei d s o f c o u p l e dp r o d u c t so n
a r . v l m o i e t i e s . S e c o n d , t h e r e i s n o e v i c l e n c ef o r i m - r e a c t i o nw i t h p r i m a r y a l k y l h a l i d e s . T h u s , c o u p l i n g o t '
p o r t a n t i n v o l v e m c n t o f m e t a l - h a l o g e ne x c h a n g e i n a p r i m a r y w i t h a s e c - a l k y lg r o u p i s b e s t a c c o m p l i s h e d
coupling reactions involving alkyl halides in ether either by reactionof a primary alkyl chloride with a
( 2 - s )G . l V I . W h i t e s i d e sa n d C . P . C a s e y ,J . A n t e r . C h e m . , S o c .E "di-sec-alkylcuprate,o " r by reaction of a primaritl'
, g.
. t 5 - Il ( 1 9 6 6 ) . alkyl bromide with a di-scc-alkyl(tri-n-butylphosphine)-
cuprate. Coupling of a primary with a t-alkyl group The mi l d condi ti ons and hi gh yi el ds associ a t edwit h
c a n b e a c c o m p l i s h e db y r e a c t i o no f a p r i m a r y a l k y l h a - thesecoupl i ng reacti onsaffordedan opportuni ty t o ex-
lide with a lithium di-r-alkyl(tri-rr-butylphosphine)cu- ami ne the stereochemi stryof carbon-carbon bond f or -
prate; this coupling fails u s i n g " d i - t - a l k y l c u p r a t e . " m a t ion during a coupling reaction. Optically active
F i n a l l y , a l t h o u g h t h e c o u p l i n g o f l i t h i u m d i a l l y l c u p r a t e (+ )-(S )-2-butanol (opti cal puri ty 77-79% ) w as pr e'
a n d l - pent y l iodide w a s a ra p i d a n d h i g h -y i e l d reac- pared by oxi dati on of the hydroborati on product f r om
t i o n . c o m p a r a b l ey i e l d s o I l - o c t e n ec o u l d b e o b t a i n e d crs-2-buteneand opti cal l y acti ve di i sopi noca m pheyl-
by direct reaction between allyllithiurn and n-pentyl borane.26 Thi s al cohol w as converted to 2-br om o-
iodide. T hus , in t hi s p a rti c u l a r c a s e ,fo rma ti o n of the ( 2 6 ) ( a ) P r e p a r e df r o m d i b o r a n e a n d ( - ) - a - p i n e n e b y t h e m e t h o d
co p p e rat e c om plexo ffe rsn o s y n th e ti ca d v a n ta g e . o f H . C . B r o w n , N . R . A y y a n g a r , a n d C ' Z w e i f e l ,J . A m e r . C h e m ' S o c "
f i c a t i o no f a p r e v i o u s l yp u b l i s h e dm e t h o d : 7w h i c h m i n -
i m i z e sr a c e m i z a t i o nb y d i s t i l l i n g t h e b r o m i d e f r o m t h e e x a m p l e ,b y n u c l e o p h i l i cd i s p l a c e m e nwt i t h i n v e r s i o no f
reac t ionm ix t ure a s i t i s fo rme d .2 r By a n a l o gyw i th the confi gurati on on the al kyl hal i de by the copper at om
w or k of S c hae fe rs aTn d re l a te d s tu d i e s b y Snyder2ew e (eq I I ), followed by collapse of the resulting forrnol
a s s um e t his ha l o g e n a ti o n p ro c e e d sw i th i nversi on of I
c o n f i g u r a t i o nt o p r o d u c e b r o m i d e o f t h e ( - ) - R c o n - R,Cu---\C-l !
f i e u r a t i o nh a v i n g [ o ] " o - 2 7 . 0 1 o ( n e a t ) ,c o r r e s p o n d i n g
t o a n o p t i c a l p u r i t y o f 7 6 t o 8 l [ , d e p e n d i n go n t h e
v alue ac c ept edfo r th e ro ta ti o n o f o p ti c a l l y p ure 2-bro- 1,, +
R . , C u ( l )l l- C \ --( + RCuu)(r )
mobutane.s0Reaction of this bromide with lithium
diphenylcuprate in refluxing ether-tetrahydrofuran c o p p e r ( l [ [ ) 3 5o r g a n o m e t a l l i cc o m p o u n d w i t h r e t e n t i o n
f i e l d e d( + ) - ( S ) - 2 - p h e n y l b u t a nhea ' , ' i n g
[cv]*-
r 7 o* 1 8 . 2 0 o f c o n f i g u r a t i o ns. 6 U n t i l m o r e i n f o r m a t i o nc o n c e r n i n g
t o + 1 8 . 7 0 " ( n e a t ) , 3 rc o r r e s p o n d i n gt o 6 7 - 6 8 % o p - both the state of aggregati onand structureof t he coppc. r
t i c a l l y 'p u r e m a t e r i a l . 3 { T h u s t h e c o u p l i n g o f l i t h i u m a t e c o m p l e x e sa n d t h e i n f l u e n c eo i a l k y l h a l i d es t r u c t u r c
d i p h e n , v l c u p r a t ew i t h 2 - b r o m o b u t a n e p r o c e e d s w i t h on the rateand stereochenlisto r yf t h e c o u p l i n gr e a c t i o n
p r e d o m i n a n ti n v e r s i o no f c o n f i g u r a t i o n . C o m p a r i s o n are avai l abl e, further specul ati on on det ailed m ech-
o i t h c o p t i c a l p u r i t i e so f t h e s t a r t i n gb r o m i d ea n d c o u - a n i s mi s p o i n t l e s s .
p l c d p r o d u c t e s t a b l i s h e st h a t t h c r e a c r i o nt a k e s p l a c e R e a c t i o no f l i t h i u m d i a l k y l c u p r a t ew s i t h a r _ r 'hl a l i d c s
w i t h 8 - l - 9 2T ; s t e r e o s e l e c t i v i tdye, p e n d i n go n t h e v a l u e d i f l e r s f r o m r e a c t i o nw i t h a l k y l h a l i d e s i, n t h a t m e t a l
a c c e p t e df o r t h e o p t i c a l r o t a t i o no f t h e e n a n t i o m e r i c a l l y h a l o g e ne x c h a n g ei s i m p o r t a n t . T h e r o l e o f t h i s n r e t a l -
p u r e2 - b r o m o b u t a n e . h a l o g e n e x c h a n g ei n n o n o x i d a t i v ec o u p l i n g o f c o p p e r
a t e c o m p l e x e sw i t h a r y l h a l i d e si s p r e s e n t l yu n c l e a r .
Discussion
I n i t i a l g e n e r a t i o no f a n a r y l c o p p e rc o m p o u n d a n d a n
T h e e x p e r i m e n t a ld a t a p r e s e n t e di n t h i s p a p e r i n d i - a l k y l h a l i d e b y m e t a l - h a l o g e ne x c h a n g em i g h t b e f i r l -
c a t e t h a t t h e r e a c t i o n o f ' l i t h i u m d i a l k y l c u p r a t e sw i t h l o w e d b y n u c l e o p h i l i cd i s p l a c e m e not f h a l i d e i o n t ' r o n r
a l k y ' lh a l i d e sp r o c e e d sw i t h o u t s i g n i f i c a nm
t etal-halogen t h e a l k y l h a l i d e b y t h e a r y l m e t a l l i cr e a g e n(t e q l 2 ) . A l -
e x c h a n g e ,b y a m e c h a n i s mw h i c h r e q u i r e s ,i n a t l e a s t . R : C u L i* A r l . - R I * A r R C u L-i - - > R A r (lll
o n e i n s t a n c ep , r e d o m i n a n ti n v e r s i o no f c o n f i g u r a t i o na t
the carbon atom originallybonded to halogen. Fur- t e r n a t i v e l y ,t h e m e t a l - h a l o g e ne x c h a n g em i g h t s i m p l ; '
ther. the structureot' the alkyl group bonded to the c o n s t i t u t e a s i d e r e a c t i o n c o m p e t i n gw i t h d i r e c t c o u -
n r e t a l a n d t o t h e h a l o g e n .t h e n a t u r e o f t h e l e a v i n g p l i n g o f t h e c o m p o n e n t s( e q l 3 ) . O u r d a t a d o n o t
g r o u p . a n d t h e p o l a r i t y o f t h e s o l v e n ta l l e x e r t a n i n - R I + A r R C u L= i - R : C u L *i A r l - > R A r (tll
f l u e n c eo n t h e c o u r s eo f t h e r e a c r i o nw h i c h i s c o n s i s t e n t
w i t h a m e c h a n i s mf o r c a r b o n - c a r b o nb o n d f o r m a t i o n p e r m i t a n u n a m b i g u o u sd i s t i n c t i o nb e t w e e nt h e s e a l -
w h i c h i n v o l v e sa n S x 2 d i s p l a c e m e nat t c a r b o n . U n - t e r n a t i v e sa t p r e s e n t . H o w e v e r , t h e o b s e r v a t i o nt h a t
d i c r _ r ' l c u p r a t easr e c a p a b l e o f n o n o x i d a t i v ec o u p l i n g
8 6 . 3 9 7 ( 1 9 6 l ) . ( b ) T h e a b s o l u t e s t e r c o c h e m i s t r yo f 2 - b u t a n o l h a s b e e n w i t h a r y l i o d i d e s e s t a b l i s h e st h a t a m e c h a n i s mf o r
cstrblishcd by rclation to lactic acid. Sce K. Wiberg, J. Amer. Chem.
S o c . , 7 4 , 3 8 9 1 ( 1 9 5 2 ) , a n d r e f c r e n c c sc i t e d t h e r e i n .
c a r b o n - c a r b o nb o n d f o r m a t i o n d o e s e x i s t w h i c h d o c s
(17) (a) J. P. Schaelcr and D, S. Wcinburg, J. Org. Chem..30, 2635 n o t i n v o l v e a n S x 2 d i s p l a c e m e not f t h e t y p e i m p l i c a t e d
( 1 9 6 5 ) ; ( b ) C . A . W i l c y , R . L . H e r s h o r v i t z .B . M . R e i n , a n d B . C .
by eq l0 and I l.
Chung, J. Amer. Chem. Soc.. 86, 9fl (196.l).
(28) The procedurc used hcrc is similar to that developed in the F r o m t h e p o i n t o f v i e w o f p o t e n t i a la p p l i c a t i o n o t '
unpublished work of F. R. Jcnsen and V. Krimsley, University of c o p p e r" a t e " c o m p l e x e si n c a r b o n - c a r b o nb o n d f o r m i n g
C u l i l o r n i a a t B e r k c l ey .
( 1 9 ) R . G . W e i s s a n d E . I . S r r v d e r .C h e m . C o m m u n . , l 3 5 8 ( 1 9 6 8 ) .
reacti ons, several practi cal l eatures of this wor k ilr e
(30) (a) P. S. Skcll, R. G. Allen, and G. Helmkamp, J. Amer. Chem. w o r t h e m p h a s i z i n g . F i r s t , t h e m o s t c o n v e n i e n tp r e p -
. S o c . .8 2 , ' l l 0 ( 1 9 6 0 ) , o b s c n ' e d [ a ] : s o 3 t . O n " l b r ( * ) - 2 - b r o m o b u t a n e a n d a r a t i o n o f t h e p r e r e q u i s i t ea t e c o m p l e x e sf r o m a s ) ' n -
calculate that the maximum value should be 39.3': (b) from the data of
R . L . L e t s i n g e r , L . G . N { a u r y , a n d R . L . B u r r v e l l ,i b i d . , 7 3 , 2 3 7 3 ( 1 9 5 1 ) , a
t h e t i cp o i n t o f v i e w i s t h a t i n v o l v i n gr e a c t i o no f 2 e q u i v
maximum valuc for [a]r,o of 34.3'ma."'be calculated; (c) F. R. Jensen of organolithium reagent with I equiv of the ap-
and D. D. Davis bclicvc thc maximum value is within the range 33.1- p r o p r i a t e c o p p e r ( l ) h a l i d e . T h i s p r e p a r a t i o ni s a p -
3-s.J". Scc D. D. Davis, Ph.D. Dissertarion. University of California
at Bcrkeley, Aug 1966: (d) P. Salvadori, L. Lardicci, and M. Stagi, p l i c a b l et o a r y l . v i n y l . a n d p r i m a r y a l k y l r e a g e n t s i. t s
R i c e r c a S c i . , 3 7 . 9 9 0 ( 1 9 6 7 ) , s h o r v t h a t S k el l ' s v a l u c s " o l 3 9 . 3 o i s t o o s u c c e s sw i t h s e c o n d a r vr e a g e n t si s m a r g i n a l , a n d i t
high. From thcir data a mlximum valuc for [.lr]lioof 35.7o may be
f a i l s w i t h t e r t i a r y r e a g e n t s . F o r c o u p l i n g r e a c t i o ns
c a l c u l a t e d ; ( c ) D . G . C o o d w i n a n d H . R . [ - l u c i s o n ,J . C h e m . S o c . ,B ,
l l 3 3 ( I 9 6 8 ) , o b s e r rc d [ a ] : : o - J 3 . ' t o t b r ( - ) - l - b r o m o b u t a n e a n d c a l - r e q u i r i n g r - a l k y l c o p p e r ( l )r e a g e n t s l. i t h i u m d i - l - a l k y ' l -
c u l a t c d e m a x i r n u n r v a l u e o t -3 { 8 c . F r o m t h c s c r c s u l t s i t a p p e a r s t h a t ( t r i - n - b u t y l p h o s p h i n e ) c o p p e r ( lc)o m p o u n d s a r e t h ' :
t h c a c t u a l v a l u c l i e s b e t r v c c n3 1 . 4 o a n d 3 - s . 7 o .
( l l ) T h c a b s o l u r c c o n t i g u r a t i o n o t ' ( * ) - ( S ) - 2 - p h e n y l b u t a n e h a s b e en (15) Cf. A. Lcvitzki and NI. Anbar. Chent. Commun.,40l (l96tl).
a s s i g n c db y 'r e l r r t i o n t o 2 - b u t a n o l , r : a n d b y r e l a t i o n t o a - p h c n y l e t h a n o l . r 3 (J6) Forrnally sirnilar oxidative addition reec!ions have becrt ttlr-
( 3 2 ) D . J . C r a m , J . A m e r . C h e n r , S o c . ,7 4 , : 1 . 1 9( 1 9 5 2 ) . servcd for a widc variety ol' dt-dt0 transition mctal complexes. Urt'
( l l ) D . J . C r a m , i b i d . , 7 4 , 2 1 3 7( 1 9 5 1 ) . fortunrtcly' thc s(ereochemistry of thcse reactions is not prescntlv
( 3 . 1 ) J . K c r r y ' o n , P . W . B . H a r r i s o n , a n d J . R . S h c ' p p a r d ,J . C h e m . S o c . , knorrrr. Cf. l. P. Collman, Accounrs Chem. Res., l, 136 (196E):
658, 661 ( 1926),reportcd [c]::o - l7.l' tbr ( - )-l-phenylbutane. L. Vaska, ibid., l,135 ( 1968).