Vanadium (II) promoted diastereo- and enantioselective intermolecular pinacol cross coupling

Article abstract of DOI:10.1016/0957-4166(90)90032-6

The cross coupling reaction promoted by [V₂Cl₃(THF)₆]₂[Zn₂Cl₆] of some aliphatic aldehydes with an aromatic aldehyde bearing a chiral auxiliary occurs in a stereocontrolled fashion to give

Full text of DOI:10.1016/0957-4166(90)90032-6

Tetrahedron: Asymmetry Vol. 1.
Printed in Great Britain
1990
Press
Va na di um ( I I ) Pr omot e d Di a s t e r e o- a nd Ena nt i os e l e c t i ve I nt e r mol e c ul a r
Pi na c ol Cr os s Coupl i ng.
Ri t a Annunz i a t a , Ma ur o Ci nqui ni ,
Ce nt r o C. N. R. a nd Di pa r t i me nt o di Chi mi c a
Mi l a no, I t a l y.
Coz z i , a nd Pa ol a Gi a r oni
I ndus t r i a l e , Vi a Gol gi 19, 20133
e
(Received 23 April
[ V Cl
a l de hy
s t e r e oc ont r ol l e d f a s hi on t o
di a s t e r e oi s ome r i c r a t i os up t o a nd e na nt i ome r i c
[ Zn Cl
of s ome
a uxi l i a r y
di ol s i n
The c r os s c oupl i ng r e a c t i on pr omot e d by
a l i pha t i c a l de hyde s wi t h a n a r oma t i c
oc c ur s i n
Abs t r a c t .
e
gi ve s yn
a
up t o 84%.
The ubi qui t ous pr e s e nc e of t he
f unc t i ona l i t y i n
a
numbe r of bi ol ogi c a l l y
a s s e mbl i ng t hi s gr oup wi t h e f f i c i e nt
Among t he a va i l a bl e pr oc e dur e s
r e l e va nt c ompounds r e qui r e s ne w me t hods f or
c ont r ol of r e l a t i ve a nd a bs ol ut e s t e r e oc he mi s t r y.
os myl a t i on of a l ke ne s oc c upi e s pr e mi ne nt pos i t i on.
I n pr i nc i pl e i nt e r mol e c ul a r pi na c ol c r os s c oupl i ng of a l de hyde s a nd ke t one s 3 r e pr e s e nt s
a
s i nc e i t doe s not r e qui r e c ont r ol of t he a l ke ne c onf i gur a t i on.
r e por t e d a n e xc e e di ngl y c onve ni e nt a l de hyde c r os s c oupl i ng
a n e ve n s i mpl e r me t hod,
Ve r y r e c e nt l y Pe de r s e n
r e a c t i on pr omot e d by t he va na di um
c ompl e x
Thi s s yn- s e l e c t i ve
ge ne r a t e d
i n f r om a nd z i nc dus t .
s ynt he s i s i s
r e ma r ka bl y a c c e l e r a t e d by a n a mi de gr oup i n ' y- pos i t i on wi t h r e s pe c t t o one of t he t wo
l i ke l y by i nt r a mol e c ul a r
e na nt i ome r i c a l l y pur e a mi de f unc t i ona l i t y c oul d a l l ow c ont r ol of
c a r bonyl s t o be c oupl e d,
We r e a s one d t ha t a n
t he a bs ol ut e
s t e r e oc he mi s t r y of t he c oupl i ng pr oc e s s , t hus gr e a t l y e xpa ndi ng i t s us e f ul ne s s . We he r e
r e por t our pr e l i mi na r y r e s ul t s i n t hi s f i e l d.
113. 7
1. 2,
by s t a nda r d f unc t i ona l gr oup ma ni pul a t i on, wa s r e a c t e d4
a l de hyde s 3- 6 i n t he pr e s e nc e of t o gi ve di ol s 7- 10. Si nc e t he
pr e pa r e d f r om pht ha l i c a nhydr i de a nd
Ami de
1
wi t h
c ombi na t i on of t hr e e s t e r e oc e nt e r s a nd of t he hi nde r e d r ot a t i on a bout t he a mi de bond
ha mpe r e d s e c ur e e va l ua t i on of t he s t e r e oc he mi c a l out c ome of t he r e a c i t on, di ol s 7- 10
a
c onve r t e d by
di a s t e r e oi s ome r i c pht ha l i de s
a
hi gh yi e l di ng
( Sc he me ) .
we r e
s moot hl y
l a c t oni z a t i on t o
mi xt ur e s of
10- 13
Ma j or i s ome r s l l a - 14a we r e
obt a i ne d by f l a s h c hr oma t ogr a phy or c r ys t a l l i z a t i on i n di a s t e r e oi s ome r i c a l l y pur e a nd
14
opt i c a l l y a c t i ve f or m a s whi t e s ol i ds .
Yi e l ds , i s ome r r a t i os , a nd e na nt i ome r i c
355

R.
al.
356
Sc he me
a
+
R - C H O
3-6
3
OH
I
-
:
;
:
HO
7-10
=
n- Pr
7, 11
a , 12
9, 13
3,
4,
R
R
=
0
2
=
6,
10, 12
=
i - Pr
16
RT,
b: PTSA, THF, RT, 15h; c :
a c e t yl
Re a ge nt s : a : 1,
di hydr oqui ni di ne , t ol ue ne , RT, 15h; d: t hi oc a r bonyl di i mi da z ol e
e : t ol ue ne , 5h.
4h;

357
Pinacol cross coupling
15
excesses
of lla-14a are collected i n Ta bl e .
As c a n be s e e n f r om t he r e por t e d
da t a t hi s me t hod c a n be a ppl i e d t o l i ne a r a nd br a nc he d a l de hyde s wi t h s i mi l a r s uc c e s s .
l e a vi ng t he di a s t e r e os e l e c t i vi t y
vi r t ua l l y unc ha nge d. The s yn r e l a t i ve c onf i gur a t i on of t he pr e domi na nt i s ome r l l a ( a nd
t hus by a na l ogy t ha t of wa s e s t a bl i s he d by pr e pa r i ng t hi s c ompound by
os myl a t i on of t he E- a l ke ne 15 i n t he pr e s e nc e of a c e t yl f ol l owe d by
Br a nc hi ng r e s ul t s i n s l i ght l y i nc r e a s e d
l a c t oni z a t i on ( Sc he me ) .
We c oul d a l s o de t e r mi ne t he a bs ol ut e c onf i gur a t i on of l l a by
16, c ompone nt of t he e s s e nt i a l oi l
c onve r s i on4 i nt o t he
a
of c e l e r y, a s de s c r i be d i n t he Sc he me .
I n c onc l us i on,
a
hi ghl y di a s t e r e o- a nd e na nt i os e l e c t i ve pi na c ol c r os s c oupl i ng r e a c t i on
ha s be e n a c c ompl i s he d f or t he f i r s t t i me by t he us e of a n i ne xpe ns i ve a nd pr a c t i c a l
r e a ge nt a nd of a uxi l i a r y. Wor k i s i n pr ogr e s s t o e va l ua t e l i mi t s a nd t he
pot e nt i a l of t hi s me t hod a nd t o e l uc i da t e t he or i gi n of s t e r e oc ont r ol .
V
a
18
Thi s s t udy
c oul d a l s o pr ovi de ne w i ns i ght i nt o t he me c ha ni s m of l ow- va l e nt me t a l pr omot e d c a r bonyl
c oupl i ng r e a c t i ons .
Ac knowl e dgme nt . Pa r t i a l f i na nc i a l s uppor t by
gr a t e f ul l y a c knowl e dge d.
Pubbl i c a I s t r uz i one
Roma i s
Ta bl e . Synt he s i s of l a c t one s
f r om a l de hyde s 2 a nd 3- 6 vi a 7- 10.
R
Di ol
Yi e l d
Yi e l d
a:b
e . e . %
n- Pr
i - Pr
7
8
73
76
72
73
86
93
77
85
2
91:
9
9
10
84
1
As de t e r mi ne d by 300 MHz
H- NMR s pe c t r os c opy.
e va l ua t e d by
s hi f t
15
r e a ge nt e xpe r i me nt s c a r r i e d out i n c ondi t i ons pr e - e s t a bl i s he d on r a c e mi c s a mpl e s .
b
Of t he ma j or i s ome r s a.
The s e
c a n be upgr a de d t o
by
a
s i ngl e
c r ys t a l l i z a t i on.

R.
et al.
358
Re f e r e nc e s a nd Not e s .
Qe vi e w: M. Na ka j i ma , K. Tomi oka , K. Koga , J . Synt h. Or g. Che m. J pn. , 47, 878, 1989.
r e por t s on s t oi c hi ome t r i c os myl a t i on: E. J . Cor e y, P. Da Si l va S.
Vi r gi l , P. - W. Yue n, R. D. J . Am. Che m. 111, 9243, 1989; T. Oi s hi , M.
J . Or g. Che m. , 54, 5834, 1989.
Re c e nt r e por t on c a t a l yt i c os myl a t i on: J . S. M. Wa i , I . Ma r ko, J . S. Sve nds e n, M. G.
E. N. J a c obs e n, K. B. Sha r pl e s s , J . Am. Che m. 111, 1123, 1989, a nd
r e f e r e nc e s t he r e i n.
Re vi e ws : Mur r y, Che m. Re v. , 89, 1513, 1989; J . M. Pons , M. Sa nt e l l i ,
Te t r a he dr on, 44, 4295, 1988. Re c e nt r e por t s : A. 0. A. Ar none , J .
55, 1240, 1990; Z. Hou, K. Ta ka mi ne , 0. Aoki , H. Shi r a hi s hi ,
H. Ta ni guc hi , J . Or g. Che m. , 53, 6077, 1988; J.-H. So, M. K. Pa r k, P.
' i nn,
J.E.
MC
Che m. ,
Or g.
Boudj ouk, J . Or g. Che m. , 53, 5871, 1988.
J.H. Fr e unde nbe r ge r , A. W. Konr a di , S. F. Pe de r s e n, J . Am. Che m.
111, 8014,
1989.
P. M. Ta ka ha r a , J . H. Fr e unde nbe r ge r , A. W. Konr a di , S. F. Pe de r s e n, Te t r a he dr on Le t t . ,
7177, 1989.
F. A. Cot t on, S. A. Dur a j , W. J . Rot h, I nor g. Che m. , 24, 913, 1985, a nd r e f e r e nc e s
t he r e i n.
_. E. Ma nz e r , I nor g. Synt h. , 21, 135, 1982.
Ende r s , P. Fe y, H. Ki ppha r dt , Or g. Synt h. ,
a l s o e a s i l y a va i l a bl e .
65, 173, 1987. The
i s
Be nz a l de hyde ga ve ma i nl y s e l f - c oupl i ng pr oduc t s , whi l e c i nna mi c a l de hyde di d not
r e a c t .
Al l ne w c ompounds ga ve a na l yt i c a l a nd s pe c t r a l da t a i n a gr e e me nt wi t h t he pr opos e d
s t r uc t ur e s .
Thi s pr oc e dur e a ppa r e nt l y doe s not a l t e r t he
c ompos i t i on of 7- 10.
I nde e d t he s yn: a nt i r a t i os de t e r mi ne d by 300 MHz
H- NMR on s ome di f f e r e nt l y
e nr i c he d s a mpl e s of 7- 10 by r e c or di ng t he s pe c t r a a t 60° C a gr e e we l l
f ound f or t he di a s t e r e oi s ome r i c mi xt ur e s of 11- 14 obt a i ne d f r om
wi t h t hos e
s a mpl e s .
Onl y 5- me mbe r e d l a c t one s we r e obt a i ne d
C=O a t 1760- 1770 c m
r e c ove r y of t he c hi r a l
I t mus t
t ha t l a c t oni z a t i on c a n
- 30. 8, m. p. 12a :
- 60. 3, m. p.
- 41. 4, m. p. 123- 125° C; 13a :
Al l r ot a t i ons a r e
- 45. 0, m. p. 131- 133° C; 14a :
0. 5 s ol ut i ons i n
c
we r e pr e pa r e d
Ra c e mi c s a mpl e s of
by t he s a me r out e s t a r t i ng f r om
The pr ot oc ol
r e qui r e d f or t he LSR de t e r mi na t i on of
151
a f f or ds l l a wi t h t he s a me a bs ol ut e
c onf i gur a t i on a nd i n a n e . e . ( 80%) ve r y s i mi l a r t o t ha t of t he pr oduc t obt a i ne d by
c r os s c oupl i ng.
M. As a mi , T. Muka i ya ma , Che m. Le t t . , 17, 1980.
Ac yc l i c c hi r a l
a na l ogous t o 2 ga ve c r os s c oupl i ng pr oduc t s wi t h
a l i pha t i c a l de hyde s wi t h be t t e r c he mi c a l yi e l ds but l owe r s t e r e oc ont r ol . The s e
r e s ul t s wi l l be r e por t e d i n t he f ut ur e .