Synthesis and Characterization of Optically Active mer-[Co(L)

Journal of the Korean Chemical Society 2002, Vol. 46, No. 4

Printed in the Republic of Korea

393



 mer-[Co(L)

](ClO

)    [L=4(S)-1- (2-pyridyl)-3-oxo-4-amino-2-azapentane(S-alaampH)  4(S)-1-(2-pyridyl)-3-oxo-4-aza-7-thiaoctane (S-metampH)]

*

  

(2002. 6. 27 )

Synthesis and Characterization of Optically Active mer-[Co(L)

](ClO

) [L=4(S)-1-(2-pyridyl)-3-oxo-4-amino-2-azapentane(S-alaampH) and

4(S)-1-(2-pyridyl)-3-oxo-4-aza-7-thiaoctane(S-metampH)]

Bae Wook Lee*, Jae-Ha Park, and Myung-Ki Doh

Department of Chemistry, Yeungnam University, Gyeongsan 712-749, Korea (Received June 27, 2002)

: , , , 

Keywords: Optically Active Ligand, Stereoselectivity, Diastereoisomer, Absolute Configuration

  !"# $% &' ( )

*+,  -./012 345 617 89:;, < =>6 ? -(-@:;A B 3 345 617 CA DEF  GHIJ KL M N OP Q2 ) RST UV.^1-3 W X YZ [\# )K% 61] 345 61A^

S_ ` a7 b# c +d^% 

Cef Eg% hi⁴ :; jJf k` l

m 6i⁵ G%n oJ lm6A p` q

 Q RSKr GV. st 6,  

 % ./A *+ gu# v <HJ

 -./ 01 wxy,⁶z{A% 

 -./ 01# Eg& DNA |% protein

t2 w1< (s7 }~EA p` ) Q2 p\# €r GV.⁷ , amidate ) *+, -

./ 012 w ‚A^ ƒA p` 7

„… †HJ DExr GV.⁸B3^, amide E

‡b ˆ‰3 # )K% ŠJ‹ s ./

017 6 ? A p` % '` ŒA 

E` Žf eC  GHIJ [‘gVr w’xy, z{  ˆ5“” ˆ•7 :;HJ– amide

E f g] |% — ˜f )K% ŠJ‹ 

f 6g&, ™q *+, †š01, amide

E ) V ›6, š01 ? polymeric 017 A d X- ›Ž œHJ f g&  5J‹ ž# Ÿ guV.^9-10 ¡ A^%  ŒA p` p\7 ` HJ ¢£¤(III) ./=A 

# )K% 4 ( amidate ) *+, 01, mer-[Co(L1)2]⁺(1) [L1=4(S)-1-(2-pyridyl)-3- oxo-4-amino-2-azapentane(S-alaampH)] mer-[Co(L²)2] (2)[L2=4(S)-1-(2-pyridyl)-3-oxo-4-aza-7-thiaoctane(S- metampH)]# 6gr, ¹³C-NMR, -(¥¦§¤X,

¨© ª(CD, Circular Dichroism)¦§¤X«7

< hiHJ ™q7 s ¬# Dg uV. ¡ ­®A^ DE, free % S-alaampH s S-metampH ™r deprotonation xS ./A

*+ gu# vA% S-alaamps S-metampJ ¯ g uV.

Journal of the Korean Chemical Society

394  

Amide E s # )K% S-alaampHs S- metampH  ? [Co(py)⁴Cl2]Cl2 ®°7 hiA B3 6guHy,¹⁰DE, „± ²ƒ2 Aldrichs FLUKA7 ³e´HJ E"µ% Že ¶ ™J D EguV.  DA DE, J^% -(¥

¦§¤X2 HP 8452 Spectrophotometer, ¨©ª

(CD, Circular Dichroism)¦§¤X2 JASCO J-715 Spectropolarimeter, ¨ œ2 FISONS EA 1108,

13C-NMR ¦§¤X2 BRUKER ARX(300 MHz)f  EguV.

mer-[Co(S-alaamp)2]ClO4(1) . 30.0 ml A·¸

A 6` S-alaampH (8.0 mmol, 2.0 g)s triethylamine 2.0 mlf )g& f ¹- Ed² Yr, 50 ml A·¸A º» [Co(py)⁴Cl2]Cl(4.0 mmol, 1.9 g)

# )`V.  ¼6E½# 70^oCJ 24² )¾9µ

²¿r, E½7 À) 20 ml F vÁK ÂÃ` VÄ A

·¸A Ų¿ NaClO⁴ 2.0 mlf )g& ÆÇrA h 8g& <Ȫ7 É-1# cS A·¸J Êˁ 4Ì gr Ͳ¿V. cSÎ 61# 500 ml 1J ÏÐ VÄ Ñ= 9K(SP-Sephadex C25, H⁺)A ¥0² Yr 1J ҁ 4Ìg& 0.1 M NaClO4J E²Y Ó `)K7 1b ,V.  # „ˆ Âò YÓ ÔÕKª7 É}Ö É-1 w,V. ×Ø;

70%. Found(%): C, 41.83; H, 4.94; N, 16.18. Calc.

for [CoC18H24N6O6Cl]: C, 42.00; H, 4.70; N, 16.32 mer-[Co(S-metamp)2]ClO4(2) . S-alaampH

ÙA S-metampH f DEg& 01 17 6

 OÚgÛ WguV. ×Ø; 50%. Found(%): C, 41.45; H, 4.96; N,13.51. Calc. for [CoC22H32N6O6S2Cl]:

C, 41.61; H, 5.08; N, 13.23.

  

# )K% 4( amidate , S-alaampH#

A·¸A^ [Co(py)⁴Cl2]Cl :;²Ü w, 61

# Ñ= 9K(SP-sephadex C25)A ¥0²¿ ›

 g]7 ÔÕKª ¥0ÝJb xÞV. cSÎ  612 ¨ œ(ßA^ [Co(S-alaamp)²]ClO47 

# )KÛ à# á  GÞr, ¹³C-¦§¤XA^ 

A âãg% CH³, CH2, CH ? C=O E A dä g% Àåf ’’ æ»C  GÞr, 120~170 ppmA

^ Àç rA âãg% · Àåf æ»èHJ é — (7 S-alaampH ) ¢Ÿ¤(III) [\.

/=A *+gr GÄ# á  GÞV(Fig. 1). |`,

, 017 -(¥ ¦§¤X2 485 nm 380 nm

Fig. 1. ¹³C-NMR spectrum of 1.

Fig. 2. Absorption and CD spectra of 1 and 2.

  mer-[Co(L)2](ClO4)    395

2002, Vol. 46, No. 4

A^ -(¥Ýf ]ê‚ÞV(Fig. 2).  oÛ ¨(

6˜) ¢Ÿ¤(III)A *+F v  017 -(¥

¦§¤X 460~475 nmA^ ]ê]% ë lgÓ

ƒ 10 nmŽì ÇíÇA^ ]ê]%n ë2 01A âãg% — ˜7 Àç rA G% π--( v®»

ëHJ w’,V. ˆî' S-alaampH A âãg

% amide E 7 ïÓKð(sp² ¼)HJ »d

facial gJ7 *+) ñ)ògIJ w,

012 mer-[Co(S-alaamp)2]⁺ (1) ó# á  GHy,  017 )ò`  (diastereo- isomer)% Fig. 3 t2 ) )ògV. '` Dô 2 Gillard «¹³ glycylglycinato(gly-gly) f Co(II)s :;²¿ ¼61# ”²Ü w, 01, [Co(gly-gly)2]⁻A^ì gly-gly ) — ˜7 ïÓ#

Ög% mer-J *+x% ë# X- ›Ž

J æ»gur, [Co(NH³)6]³⁺ ? [Co(CO³)3]³⁻ 4(

 (gly-gly)s7 89:;HJ w, [Co(gly- gly)2]⁻ì t2 ›f ]ê‚ÞHy, Lappin «¹⁴ 4 (

J õö¤x% dipeptide q *+, Ni01, [Ni(gly-gly)2], [Ni(gly-ala)2], [Ni(ala-gly)2], [Ni(ala-ala)2]

„—) meridional Ö÷J *+ ,Vr r` Dô

Ú8`V.

|`, 01 17 (absolute configuration)f ሏ +g& CD¦§¤X# Dgur(Fig. 2), ™ øA^ ù  Gú 480 nmA^ K*<» Ä7 CD¦

§¤X# ]ê‚r GV. Gillard¹⁵% mer-[Co(L-phe- gly)2]⁻ 017 A p` A^ Ä= 9

KJ mer-[Co(L-phe-gly)²]⁻7 f

` › ûË Eü, S(C²) % 500 nm  {A^ g]7 Ä7 CD ¥Ýb ]ê]% :Ó, ýg Û ¥0, R(C²) % 
þA^ Ä7 CD) ] ê]% ë2 tH] 570 nmA^ Ñ7 CD ¥Ý) ]

ê]% ë Vÿy, S(C2)7 j
ÕA G

% proton hð rA 7d l` ŽìJ
ð#

€HIJ   E ,Vr guV. ˆî' [Co(L- gly-gly)2]⁻ 01A^ì 570 nmA^ Ñ7 CD¦§¤X

ýgÛ ]êL f Λ-(+)-[Co(L-gly-gly)2]» ë HJ rguV. |`, Mckenzie «¹⁶ì Na³[Co(CO)3]

· 3H2Os ˆ5“” ê ›6, 4( 

glycyl-L-leucine(gly-L-leu), L-alanyl-glycine(L-ala-gly), L-alanyl-L-alanine(L-ala-L-ala) *+, ¢Ÿ¤(III)0 1, [Co(gly-L-leu)2]⁻, [Co(L-ala-gly)2]⁻ ™r [Co(L- ala-L-ala)2]⁻7 # CD ¦§¤XHJ D`

› Ä7 ~b ]ê]% 01 cS %n, ë2

— [ `)Kb wx v®3r eP guV. Martin «¹⁷2 [Co(gly-L-ala)²]⁻(A), [Co(gly-L- leu)2]⁻(B), [Co(L-phe-gly)2]⁻(C)A âãg%  |%

ÕA 7d w % PMR Àå7 J–

— 7 wlØ# ”` › R(C²)/

S(C2)% ’’ A=58/42, B=66/33 ™r C=70/30HJ ]ê V. `©, Boas «¹⁸2 [Co(L-ala-L-ala)2]⁻f VÑ

` hiHJ 6g& w, mer-f `

› 6hiA B3 wl) @3Ky, Co(III) hydroxide oxideJ– 6gu# v ` )K 

b cSÎVr guV. ¡ 7 j
A^ì 6

` 01 1 X åJ™À A 7d g]7 1Jb xÞ%n ë2 Mckenzie «¹⁶7 

›s Ú8gy, CD¦§¤X Ä7 ~b# ]ê‚

% ëHJ ˆ Gillard¹⁵) eP` — )K  [ A^ S(C2) ) wx% ëHJ w’,V.

`©, S-metampH f A·¸A^ [Co(py)⁴Cl2]Cl

 :;²Ü w, 617 -(¥¦§¤Xì Fig.

2A^ ù  Gú 01 1 7 OÚ` ¥Ýf ] ê‚ÞV. |`, ¹³C-¦§¤XHJ– — (7 S- metamp ) ¢Ÿ¤(III) [\ ./=A *+ g uHy(Fig. 4), w, 01 mer-[Co(S-metamp)2]⁺ (2)» ë# á  GÞV. ™'], Fig. 2A ]ê ëW X 01 27 CD ¦§¤X2 480 nmA^ Ä7 CD ¦

§¤X ]ê]% ë2 01 1 tH], V ÇíÇ

þ» 570 nmA^ Ñ7 CD ¦§¤X# ]ê‚ÞV.

s t2 ›A R(C²)s S(C²)f CD ¦§¤XHJ ` Gillard<sup>15</sup>7 rf r`V Ó, 01 2% R(C²)» ëHJ ,V. B3

^ ¡ A^%  # )K% YZ 4(

Fig. 3. The structure of diastereoisomer of 1 and 2.

Journal of the Korean Chemical Society

396  

amidate , S-alaampHs S-metampH) *+, 0 1 1 2f cÞHy, X åJ™À hiHJ

` )K b x% ë# á  GÞV. ˆ î' CD ? -(¥¦§¤X (ßJ– ê › 6A 7d w, lm 4 ( ) <

HJ *+xS S(C2)-mer-[Co(S-alamp)2]⁺s R(C2)-mer- [Co(S-metmp)2]⁺7 f ’’ )K% ëHJ w

’guV.

¡ % Νã†(KRF-2001-005-D20013)  lA 7d RS Hy, A Df ‰V.

   

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Fig. 4. ¹³C-NMR spectrum of 2.