Stereochemistry of Optically Active Transition Metal Compounds

17

Stereoselective Synthesis of Quadridentate Ligands U t i l i z i n g a Template Reaction of M e t a l Complexes

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M. SABURI, T. MAKINO, K. HATA, Κ. MIYAMURA, and S. YOSHIKAWA Department of Synthetic Chemistry, Faculty of Engineering, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan Curtis and coworkers first reported the amine-imine linkage formation of the type shown in Figure 1 by condensation of two molecules of acetone with ethylenediamines in the presence of nickel(II) or copper(II) ions (1, 2, 3). It was also shown that this type of reaction generally occurs with several carbonyl compounds (4, 5). Later, the mechanism of the linkage formation and the stereoisomerism and some reactions of the metal complexes with macrocycles were investigated in detail (5, 6, 7). Further, it should be noted that the same macrocycle as in Figure 1 could be obtained by using condensation dimers of acetone, such as diacetone alcohol or mesityl oxide (8). It was also found that several kinds of α,β-unsaturated ketones and ß-hydroxyketones may be used to prepare macrocyclic diamino -diimines (8). This observation is very important, because by using suitable ketones it becomes possible to introduce desired substituent(s) into the three carbon atom linkage. In fact, a variety of diamino-diimine macrocycles has been prepared and used as ligands in recent years (9 - 14). However, almost a l l of the macrocycles were synthesized under reaction conditions not requiring metal ions such as nickel(II). The use of substituted 1,2-diamines in place of ethylenediamine gave another possibility to increase the variety of macrocycles. Studies by some researchers, using racemic (3, 15) or optically active (15, 16) propylenediamine produced macrocyclic and open-chain ligands, as shown in Figure 2. However, this is the only example which succeeded in formation of this linkage, using chiral diamines. An attempt to use butane-2,3-diamine or stilbenediamine was reported to be unsuccessful (3). On the other hand, some amine compounds have been found to give open-chain quadridentate ligands by reaction with acetone (3, 17, 18, 19, 20). It is noteworthy that the copper(II) complex of N-hydroxyethylethylenediamine, which has a primary and a secondary amino group, gives a single-bridged ligand by reaction with acetone (19, 20). This observation is of much 0-8412-0538-8/80/47-119-325$05.00/0 © 1980 American Chemical Society

Douglas and Saito; Stereochemistry of Optically Active Transition Metal Compounds ACS Symposium Series; American Chemical Society: Washington, DC, 1980.

STEREOCHEMISTRY OF TRANSITION METALS

326

i m p o r t a n c e b e c a u s e i t seems t o s u p p o r t t h e v i e w t h a t some N - m o n o s u b s t i t u t e d 1,2-diamines w i l l g i v e r i s e t o t h e c o r r e s p o n d i n g o p e n - c h a i n t r i a m i n o - i m i n e s by c o n d e n s a t i o n r e a c t i o n s w i t h ketones i n the presence of metal i o n s . I n T a b l e I a r e l i s t e d t h e s t r u c t u r e s and a b b r e v i a t i o n s o f the c h i r a l N - s u b s t i t u t e d 1,2-diamines and t h e k e t o n e s u s e d i n t h i s r e p o r t . Our i n v e s t i g a t i o n s t a r t e d w i t h t h e e x p e c t a t i o n t h a t o n l y t h e p r i m a r y ami no group o f t h e s e d i a m i n e s w o u l d be i n v o l v e d i n the condensation r e a c t i o n s w i t h the ketones used. R e a c t i o n s o f N i ( S - a m p r ) % I o n w i t h K e t o n e s (21). Initially, the r e a c t i o n s o f t r i s ( 2 ( S ) - a m i n o m e t h y l p y r r o l i d i n e ) n i c k e l ( I I ) ( N i ( S - a m p r ) ^ ) w i t h MVK and HBO w e r e e x a m i n e d . The c o n d e n s a t i o n r e a c t i o n s were c a r r i e d out i n methanol under the c o n d i t i o n s i n d i c a t e d i n T a b l e I I , and r e a c t i o n p r o d u c t s w e r e s e p a r a t e d f r o m o t h e r compounds by SP-Sephadex c a t i o n e x c h a n g e c h r o m a t o g r a p h y . The p r o d u c t s w e r e c o l l e c t e d and p u r i f i e d as t e t r a p h e n y l b o r a t e o r tetrachlorozincate salts. The s e p a r a t i o n and p u r i f i c a t i o n p r o c e d u r e s a r e a l m o s t t h e same t h r o u g h o u t t h e s e v e r a l r e a c t i o n s w i l l be d e s c r i b e d h e r e . I n t h i s way, two k i n d s o f n i c k e l ( I I ) c o m p l e x e s w e r e o b t a i n e d f r o m r e a c t i o n m i x t u r e s w i t h e i t h e r MVK o r HBO (See Scheme 1). The s t r u c t u r e s o f t h e s e c o m p l e x e s ( F i g u r e 3) a r e most e f f e c t i v e l y d i s t i n g u i s h e d by I R m e a s u r e m e n t s , t h e d e t a i l s of w h i c h w i l l be r e p o r t e d e l s e w h e r e (21). A few i n t e r e s t i n g m a t t e r s a r e n o t i c e d f r o m t h e r e s u l t s i n T a b l e I I . The f i r s t i s t h a t i n a d d i t i o n t o t h e e x p e c t e d c o m p l e x i n w h i c h a m i n e - i m i n e l i n k a g e s c o n n e c t p a i r s o f p r i m a r y amino g r o u p s ( t y p e C i n F i g u r e 3), t h o s e i n w h i c h t h e l i n k a g e c o n n e c t s a p r i m a r y and a s e c o n d a r y amino group ( t y p e A o r B) a r e p r o d u c e d . I f o n l y t h e p r i m a r y amino g r o u p w e r e i n v o l v e d i n t h e s e r e a c t i o n s , the t y p e C c o m p l e x m i g h t be t h e s o l e p r o d u c t . The r e a s o n f o r the f o r m a t i o n o f t y p e A and Β c o m p l e x e s w i l l be d i s c u s s e d l a t e r . The s e c o n d i m p o r t a n t m a t t e r i s t h a t t h e d i s t r i b u t i o n o f the p r o d u c t s i s d i f f e r e n t b e t w e e n r e a c t i o n s w i t h MVK and HBO. I n t h e MVK r e a c t i o n , l i n k a g e f o r m a t i o n t a k e s p l a c e e x c l u s i v e l y b e t w e e n p r i m a r y and s e c o n d a r y amino g r o u p s , w h i l e i n t h e HBO r e a c t i o n such s e l e c t i v i t y i s not observed. F u r t h e r , i t s h o u l d be n o t e d t h a t i n t h e r e a c t i o n w i t h HBO, no m a c r o c y c l i c c o m p l e x was f o r m e d , d e s p i t e t h e f a c t t h a t t h e t y p e Β c o m p l e x was a c t u a l l y o b t a i n e d . I t was r e a d i l y c o n f i r m e d t h a t t h e Β c o m p l e x (Rx, R2 = Η ) , a f t e r b e i n g i s o l a t e d , c o u l d be c o n v e r t e d t o t h e m a c r o c y c l e A ( R i , R2 = H) by r e a c t i o n w i t h MVK. T h e r e f o r e , t h e d i f f e r e n c e i n r e a c t i v i t y b e t w e e n MVK and HBO i s o b v i o u s . Table I I a l s o i n c l u d e s the r e s u l t s of the r e a c t i o n s of Ni(S-ampr)§ w i t h some o t h e r k e t o n e s ; i . e . , MNPK, HPO, MOX, and DAA. I t i s i n t e r e s t i n g t h a t w i t h these ketones the amine-imine l i n k a g e c o n n e c t s s e l e c t i v e l y t h e p r i m a r y amino g r o u p s o f two d i a m i n e s . L i n k a g e f o r m a t i o n b e t w e e n a p r i m a r y and a s e c o n d a r y amino group no l o n g e r o c c u r s . I t s h o u l d be n o t e d t h a t t h e s e +

+

+


17.

SABURi E T A L .

Quadridentate

Ligands

327

T a b l e I . S t r u c t u r e s and A b b r e v i a t i o n s o f C h i r a l and K e t o n e s Name

1,2-Diamines

Abbreviation

Structure

2(S)-2-aminomethy1pyrrolidine

S-ampr H

2 (R) - 2 - a m i n o m e t h y l pipelidine

CH NH 2

2

CH NH

2

2

R-ampi

H 3(S)-3-aminopipelidine 3(S)-3-aminohexahydroazepine diacetone

alcohol

S-apip -NH. H

S-ahaz

H ( C H J - Ç - C H -Ç-CH OH 0

DAA

(CH ) C=CH-C-CH

MOX

?

J

mesityl

oxide

methyl v i n y l ketone

3

2

CH =CH-C-CH 0

2

4-hydroxy-2-butanone

8 A

3

MVK

Q

3

HBO

1A

2" 2

methyl n-propenylketone

CH -CH=CH-C-CH 3 β 3

MNPK

4-hydroxy-2-pentanone

CH -ÇH-CH -C-CH OH 0

HPO

°1 °2

0

Q

M i x t u r e o f c i s and t r a n s i s o m e r s The r a c e m i c m i x t u r e



328

CH H C^ r /

C

3

z^2

m

H

C

Λ

CH3-..

3

2-dL H

3

^ 4 H2O

CH / \ /H2 NH If I II H ^ C — C 2

N

NH

2

NH

2

(II)

Figure 1.

Condensation reaction of metal(II)-ethylenediamine complexes with acetone. (Only one of the products is shown.)

ι IL

II

k

If

L/A^

c

Ν

c

ι

A

A c X

Ν

A

M

\

Ν

h

C

c

^K / -c

1

X

I

Γ

A -

r

il

I

Ν

N

L

V

C

f X

(Al^ A c Figure 2.

Condensation reaction of metal(îl)-propylenediamine acetone (M=Ni(II) or Cu(II))

complexes with

Figure 3. Reaction products of S-ampr complexes with some ketones (M=Ni(II) or Cu(II)); for reaction with MVK or HBO, R, and R = H; with MNPK or HPO, R, = Hi and R = CH ; with MOX or DAA, R, and R = CH . 2

2

3

2

3


17.

SABURI

ET

AL.

Quadridentate

Ligands

329

four ketones have a t l e a s t one methyl group on the carbon atom 3 to the carbonyl group. So i t can be a n t i c i p a t e d that some s t e r i c e f f e c t i s at work i n the linkage-forming r e a c t i o n . Reactions of Cu(S-ampr)% Ion with MVK and DAA. (22) S i m i l a r l i n k a g e formation r e a c t i o n s took place f o r copper(II) complex of S-ampr. In Table I I are shown the r e s u l t s w i t h MVK and DAA. Again i n the case of DAA, only the type C complex was formed; that i s , only the primary amino groups were concerned i n the condensation. On the other hand, a l l three complexes generated i n the MVK r e a c t i o n . Among these complexes, the macrocycle (A) was the main product,, and the y i e l d s of the others (B and C) were very low. Thus, i n the MVK r e a c t i o n , l i n k a g e formation seems to occur c h i e f l y between a primary and a secondary amino group, as i n case of the n i c k e l ( I I ) complex. The s t e r e o s e l e c t i v i t y among A, Β and/or C observed i n the linkage formation r e a c t i o n s of S-ampr complexes i s explained e s s e n t i a l l y as f o l l o w s , taking some s t e r i c f a c t o r s i n t o c o n s i d e r a t i o n . There are two p o s s i b l e gauche conformations i n which the S-ampr may coordinate to a metal i o n , namely the δ and the λ conformers. As shown i n F i g u r e 4, the s u b s t i t u e n t s on the Ν and C atoms have d i f f e r e n t o r i e n t a t i o n s from one another i n these δ and λ conformations. From a stereochemical view, the δ conformation w i l l be more p r e f e r a b l e than the λ. F i g u r e 4 a l s o shows two modes of l i n k i n g two molecules of S-ampr. In the case where both the primary amino groups are connected (Figure 4b ) , no s e r i o u s s t e r i c r e p u l s i o n s are found, even i f R\ and/or R2 are methyl groups. However, i n the case i n which the l i n k a g e connects a primary and a secondary amino group (Figure 4-a), s t e r i c r e p u l s i o n occurs between C-substituents at the l i n k a g e and the p y r r o l i d i n e r i n g of S-ampr, i f the s u b s t i t u e n t Ri i s a methyl group. Therefore, i f both R\ and R2 i n F i g u r e 4-a are protons, a l i n k a g e connecting a primary and a secondary amino group w i l l be f a v o r e d . In these terms, the r e s u l t s given i n Table I I are reasonable because only with MVK or HBO can the amine-imine bridge occur between primary and secondary amines; with other b r i d g i n g reagents, complexes having such s t r u c t u r e s are not formed at a l l . +

Reactions of Cu(II) Complexes of S-apip and S-ahaz. (22, 23) Experimental r e s u l t s on l i n k a g e formation, which were obtained by u s i n g S-apip and S-ahaz as diamines, give f u r t h e r i n f o r m a t i o n about t h i s kind of condensation. Both diamines, S-apip and S-ahaz, can act as b i d e n t a t e l i g a n d s when amino group at 3 p o s i t i o n of the r i n g takes the a x i a l o r i e n t a t i o n . F u r t h e r , an i n t e r e s t i n g f e a t u r e of these diamines as l i g a n d s f o r the copper(II) i o n has been recognized (24). As i l l u s t r a t e d i n Figure 5, there are two geometrical ways of c o o r d i n a t i o n ; c i s and t r a n s . In the c i s form, where the primary and secondary amino groups take p o s i t i o n s c i s to one another, the two a p i c a l p o s i t i o n on the copper(II) i o n are considered to be blocked from the c o o r d i n a t i o n because of the presence of the diamine s k e l e t o n ,



330

Figure 5.

Geometrical isomers (trans and cis) of Cu(II) complexes of S-apip and S-ahaz


17.

SABURI ET AL.

Quadridentate

Ligands

331

so t h a t t h e c o m p l e x w i l l h a v e a f o u r - c o o r d i n a t e d s t r u c t u r e . I n t h e t r a n s f o r m , one o f t h e a p i c a l p o s i t i o n o f c o p p e r ( I I ) i s open f o r c o o r d i n a t i o n w i t h s u c h l i g a n d s a s h a l i d e s o r s o l v e n t s . On t h e b a s i s o f s p e c t r o s c o p i c a n d c o n d u c t i v i t y m e a s u r e m e n t s , some e v i d e n c e h a s b e e n o b t a i n e d s u p p o r t i n g t h i s s u g g e s t i o n t h a t the c o p p e r ( I I ) complexes o f these diamines p r e f e r a b l y take t h i s f i v e c o o r d i n a t i o n s t r u c t u r e , e v e n t h o u g h a v e r y s m a l l amount o f the c i s s t r u c t u r e i s probably present a t e q u i l i b r i u m (24). Therefore, i t i s expected that i f the f i v e - c o o r d i n a t e d s t r u c t u r e i s m a i n t a i n e d d u r i n g l i n k a g e f o r m a t i o n w i t h k e t o n e s , the main p r o d u c t s w i l l have s t r u c t u r e s i n w h i c h p r i m a r y a n d s e c o n d a r y amines a r e connected r e g a r d l e s s o f the p a r t i c u l a r k e t o n e s u s e d . T h i s i s because s t e r i c r e p u l s i o n s found i n the c o n d e n s a t i o n r e a c t i o n s b e t w e e n S-ampr a n d k e t o n e s o t h e r t h a n MVK a n d HBO, seems n o t t o o c c u r i n t h e s e d i a m i n e c o m p l e x e s . The r e s u l t s o f t h e c o n d e n s a t i o n r e a c t i o n s f o r S - a p i p and S-ahaz C u ( I I ) c o m p l e x e s a r e s u m m a r i z e d i n T a b l e I I I . The s t r u c t u r e s o f p r o d u c t s , A, B, and C i n T a b l e I I I a r e i l l u s t r a t e d i n F i g u r e 6 f o r the case o f S-apip. A few i n t e r e s t i n g f a c t s a r e r e c o g n i z e d from these d a t a . As f a r a s S - a p i p a n d S-ahaz a r e c o n c e r n e d , p r o d u c t s w i t h l e s s crowded k e t o n e s s u c h a s MVK, HBO, MNPK, o r HPO h a v e , w i t h o u t e x c e p t i o n , t h e a m i n e - i m i n e l i n k a g e formed b e t w e e n p r i m a r y a n d secondary amines. Hence, t h e p r o d u c t s a r e e i t h e r A o r B, o r sometimes b o t h o f them, a s i n t h e c a s e o f S-apip-MNPK and S-ahaz-MVK. F u r t h e r , t h e y i e l d s a r e n o t s o b a d . Therefore i t i s very probable that l i n k a g e f o r m a t i o n takes p l a c e , almost e x c l u s i v e l y , on the f i v e - c o o r d i n a t e d s t r u c t u r e o f c o p p e r ( I I ) , as e x p e c t e d a b o v e . Such s e l e c t i v i t y due t o t h e c o o r d i n a t i o n mode a b o u t c o p p e r ( I I ) i o n w i l l n o t w o r k w e l l i n t h e c a s e o f t h e S-ampr c o m p l e x , b e c a u s e o f i t s s t r u c t u r e , s o t h a t a s m a l l amount o f type C i s o b t a i n e d . Remarkable d i f f e r e n c e s a r e found between the r e s u l t s f o r MOX o r DAA and o t h e r k e t o n e s . W i t h t h e s e a c e t o n e d i m e r s , no m a c r o c y c l i c p r o d u c t was o b t a i n e d . I n t h e c a s e o f S - a p i p a n d S-ahaz, t h e y i e l d o f o t h e r p r o d u c t s (B and C) a r e a l s o v e r y l o w . T h i s p r o b a b l y i n d i c a t e s t h e e f f e c t s o f some s t e r i c f a c t o r s , which reduce the r e a c t i v i t y . The s t e r i c f a c t o r w i l l b e due c h i e f l y t o r e p u l s i o n s b r o u g h t a b o u t by two m e t h y l g r o u p s i n k e t o n e s . The r e p u l s i o n w o r k s i n t h e t r a n s i t i o n s t a t e f o r f o r m a t i o n o f b o t h Β a n d C, so t h a t t h e y i e l d o f e a c h f o r S - a p i p and S-ahaz i s l o w e r e d . The f o r m a t i o n o f t y p e C p r o d u c t s f o r S - a p i p a n d S-ahaz i s r a t h e r s u r p r i s i n g , b e c a u s e t h e s e s u b s t a n c e s s h o u l d be g e n e r a t e d through t h e f o u r - c o o r d i n a t e d - c o p p e r ( I I ) complexes. The f o u r c o o r d i n a t e d s p e c i e s a r e c o n s i d e r e d t o be p r e s e n t i n o n l y a s m a l l r a t i o compared w i t h t h e f i v e - c o o r d i n a t e d s p e c i e s , a s d i s s c u s s e d earlier. Therefore, theformation o f C f o r these diamines ( S - a p i p and S-ahaz) seems t o s u g g e s t t h e l o w r e a c t i v i t y o f acetone dimers towards t h e i r f i v e - c o o r d i n a t i o n complexes.


STEREOCHEMISTRY

3 3 2

Table I I .

Complex

°1 °2

O F

TRANSITION

Products D i s t r i b u t i o n f o r Reactions o f N i ( I I ) - o r C u ( I I ) - S - a m p r Complexes w i t h S e v e r a l K e t o n e s Ketone

Reaction Time(hr.)

Temp.(°C)

MVK 20 HBO 65 MNPK 65 HPO 65 MOX 105 DAA 105 MVK 65 DAA 65 Structures o f Products A(34%);B(5%);C(4%)

[Ni(S-ampr) ](C10 ) 3

4

0

MVK

1

Products

A 24 Β 6 4 6 7 7 A 2 10 are indicated

(Total Yield)

+ Β (69%) + C (47%) (69%) C C (51%) (53%) C (77%) C + Β + C (43%)°2 (80%) C i n F i g . 3 a n d Scheme 1

A + Β (R ,R =H)

2

1

HBO

2

Β + C (R R =H) r

Scheme 1.

Table I I I.

Lieand XJ

ο

LAvL

METALS

2

MNPK o r HPO

C

(R^H.R^C^)

MOX o r DAA

C

(R ,R =CH ) 1

2

3

Reactions of [Ni(S-ampr) ](ClO )2 with ketones. (A, Β, and C are indicated in Figure 3.) 3

Jl

Products D i s t r i b u t i o n f o r Reactions o f C u ( I I ) S - a p i p o r -S-ahaz Complexes w i t h K e t o n e s ( a t 65°C)

Ketone

Reaction Time ( n r . )

A

Yield(%J Β

MVK 2 76 HBO 6 9 S-apip MNPK 2 3 HPO 6 0 MOX 11 0 DAA 11 0 S-ahaz MVK 2 43 DAA 10 0 °1 S t r u c t u r e s o f A,B,C a r e i l l u s t r a t e d

1 58 43 47 3 8 13 4 i n Fig.6

°1 C 0 0 0 0 2 12 0 3


17.

SABURi E T A L .

Quadridentate

Ligands

333

F u r t h e r , t y p e C c o m p l e x e s o f S - a p i p a n d S-ahaz s h o u l d h a v e a s e v e r e s t e r i c r e p u l s i o n b e t w e e n t h e m e t h y l group a t t h e l i n k a g e a n d t h e s i x - o r seven-membered r i n g a x i a l l y s u b s t i t u t e d t o t h e f i v e - m e m b e r e d c h e l a t e r i n g s . T h u s , t h e y m i g h t have some d i s t o r t e d s t r u c t u r e s , such as a c i s - 3 form, i n s t e a d o f t h e p l a n a r s t r u c t u r e , a l t h o u g h t h e p o s s i b i l i t y has n o t b e e n c o n f i r m e d as y e t . Another important stereochemical f a c t o r working i n l i n k a g e f o r m a t i o n i s t h e e f f e c t o f t h e d i r e c t i o n o f t h e N-H bond o n t h e secondary n i t r o g e n . For a l l o f the diamines d e s c r i b e d so f a r ; i . e . S-ampr, S - a p i p , a n d S-ahaz, t h e N-H bond i s e q u a t o r i a l i n c h a r a c t e r , a s shown i n F i g u r e 7. 2(R)-2-Aminomethylpipelidine (R-ampi), another N - s u b s t i t u t e d c h i r a l 1 , 2 - d i a m i n e , h a s a v e r y s i m i l a r s t r u c t u r e t o t h e S-ampr, b u t t h e N-H bond f o r t h e c o o r d i n a t e d R-ampi s h o u l d p r e f e r a b l y have a n a x i a l d i r e c t i o n . I t i s p o s s i b l e t o suppose a c o o r d i n a t i o n s t r u c t u r e h a v i n g a n e q u a t o r i a l N-H b o n d , a s i l l u s t r a t e d i n F i g u r e 7. However, s u c h a s t r u c t u r e w i l l be l e s s s t a b l e t h a n t h a t w i t h t h e a x i a l N-H b o n d . I n f a c t , b y a r e a c t i o n o f i t s c o p p e r ( I I ) c o m p l e x w i t h MVK, R-ampi gave two open c h a i n p r o d u c t s , w h i c h c o r r e s p o n d t o t h o s e i n d i c a t e d a s F i g u r e 3-B and C f o r t h e c a s e o f S-ampr c o m p l e x . The y i e l d s w e r e v e r y l o w . Furthermore, i n t h i s case t h e f o r m a t i o n o f t h e m a c r o c y c l i c p r o d u c t was t o o s m a l l t o b e i s o l a t e d , e v e n i f i t were f o r m e d . T h i s i s i n c o n t r a s t t o t h e o b s e r v a t i o n t h a t m a c r o c y c l e s were t h e m a i n p r o d u c t s f o r t h e o t h e r d i a m i n e s upon r e a c t i o n s w i t h MVK. T h u s , t h e r e a c t i v i t y o f R-ampi i s o b v i o u s l y much l o w e r t h a n t h a t o f S-ampr t o w a r d MVK i n t h e p r e s e n c e o f c o p p e r ( I I ) i o n . The d i f f e r e n c e i n r e s u l t s b e t w e e n t h e s e d i a m i n e s c o u l d n o t b e e x p l a i n e d , i f t h e e f f e c t o f t h e N-H bond d i r e c t i o n w e r e n o t t a k e n i n t o c o n s i d e r a t i o n . T h i s i s one o f r a r e e x a m p l e s w h i c h show t h a t t h e d i f f e r e n c e i n t h e o r i e n t a t i o n o f t h e N-H b o n d , e q u a t o r i a l o r o x i a l , w i l l d e c i d e i t s r e a c t i v i t y i n m e t a l complex reactions. Summary T h i s r e p o r t i s concerned w i t h the s t e r e o s e l e c t i v i t y o f t h e c o n d e n s a t i o n r e a c t i o n s o f some c h i r a l N - s u b s t i t u t e d 1 , 2 - d i a m i n e s w i t h a,3-unsaturated ketones o r 3-hydroxyketones u s i n g n i c k e l ( I I ) or copper(II) ions as the templates. Throught the r e a c t i o n s , s t e r i c r e p u l s i o n s between the s u b s t i t u e n t s o f diamines and those on k e t o n e s a f f e c t m a i n l y t h e s e l e c t i v i t y o f l i n k a g e f o r m a t i o n . I n the case o f the c o p p e r ( I I ) - t e m p l a t e r e a c t i o n , the i n f l u e n c e o f c o o r d i n a t i o n modes o f t h e d i a m i n e s a r o u n d t h e m e t a l i o n i s a l s o o b s e r v e d . The i m p o r t a n c e o f t h e d i r e c t i o n o f t h e N-H bond at the c o o r d i n a t e d secondary n i t r o g e n i s r e c o g n i z e d ; t h e e q u a t o r i a l N-H bond i s s u f f i c i e n t l y r e a c t i v e f o r r e a c t i o n w i t h k e t o n e s , w h i l e t h e a x i a l N-H seems t o be a l m o s t u n r e a c t i v e .



334

Figure 7.

Conformations of coordinated N-substituted chiral 1,2-diamines


17.

SABURI ET AL.

Quadridentate Ligands

335

Literature Cited 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24.

Curtis, Ν.F., J. Chem. Soc., (1960) 4409 Curtis, Ν.F., and House, D.A., Chem. and Ind., (1961) 1708 Blight, M.M., and Curtis, N.F., J. Chem. Soc., (1962) 3016 House, D.A., and Curtis, N.F., J. Am. Chem. Soc., (1964) 86, 1331 Curtis, N.F., Coord. Chem. Rew., (1968) 3, 3 Curtis, N.F., J. Chem. Soc. Dalton, (1972) 1357 Lindoy, L . F . , and Busch, D.H., Prep. Inorg. Reac., (1971) 6, 1 MacDarmott, T . E . , and Busch, D.H., J. Am. Chem. Soc., (1964) 89, 5780 Curtis, N.F., and Hay, R.W., Chem. Commun., (1966) 524 Kolinski, R.A., and Korybut-Daszkiewicz, B., Inorg. Chem. Acta, (1975) 14, 273 Hay, R.W., and Lawrence, G.A., J. Chem. Soc. Dalton, (1975) 1466 Hay, R.W., and Jerahg, B., J. Chem. Soc. Dalton, (1977) 1261 Hay, R.W., Piplani, D.P., and Jeragh, B., J. Chem. Soc. Dalton, (1977) 1951 Cook, D.F., Curtis, N.F., and Hay, R.W., J. Chem. Soc. Dalton, (1973) 1160 Curtis, N.F., J. Chem. Soc. Dalton, (1973) 863 Ito, H . , and Fujita, J., Bull. Chem. Soc. Jpn., (1971) 44 741 Patel, V.C., and Curtis, N.F., J. Chem. Soc. (A), (1968) 1265 Curtis, N.F., J. Chem. Soc. Dalton, (1975) 91 Patel, V . C . , and Curtis, N.F., J. Chem. Soc. (A), (1969) 1607 Hughes, M.N., Underhill, Μ., and Rutt, K.J., J. Chem. Soc. Dalton, (1972) 1219 Makino, T . , Saburi, Μ., and Yoshikawa, S., to be submitted. Miyamura, Κ., Makino, T . , Hata, Κ., Saburi, Μ., and Yoshikawa, S., to be submitted. Makino, T . , Hata, Κ., Saburi, Μ., and Yoshikawa, S., 287 Chem. Lett., (1979) Morita, M., Mizoguchi, Y . , Saburi, Μ., and Yoshikawa, S., to be submitted.

RECEIVED October 4, 1979.


Stereochemistry of Optically Active Transition Metal Compounds

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