DRLIGPAQ–c|

qW
mw

os›iltl¯z–“tl¨v

6(93

z–“6Ž2_c“@–c|)=%1#œ;>/=#DRLIGPAQ–c|16®Xjtlš} ‘@˜/z–“5–c| «@g'ƒ'_c“@z–“3–—&+=~¥0=”3`‹–“ 3!/:-1:hŽ2TU©—“@Z=%1#œ;>/=‚¡£3!/6 u´";KBM PFH–“ª1

{11:3DRLIGPAQ–c|~¥#¬r',ˆ¨¢06‚¡£5–“

ª–—3!$=DRLIGPAQ–c|~¥3./§)=

¸KBMPFH–“ª

z–“5TU©–c|ž@˜/ƒ'–“ª @Z=1

CH2OH O OH

~¥6®Xjtl~¥#™­)=V\"

;ke'/,bš36  u3AOJCPDE OH

H5   –—£5    –c|²± Š 3    ¦ p Y @ ’ ^ f µ ' / y ,

CH2OH O

 ¶d¸·#†[0=¸·%5Ž2„‘@ ¤

O CH2NH 2 OH

j€Z~¥#‡™­5…U362"2"ig2ZŒ0

 u3i‰;5CQSN#–c|²±Š@ay)= "?)L' §B2?>)Mùõ(¶A'ÖñµkqW]Sb>)MRU^etvZuBǒ¬æ


 

Wo
HK$  ${w*>2‰›x4( ¤v§¦¥

+'1'5  5šn4—}*>˜az@’9„#?7Š‘…5ž(;cŠ‘5g¢@p* >'2$t•1!>

  KLO3$*/6OEN8MH@PMafŒ°i²³±"$l#kfJNC6O9 FP?«p‰y3$*Ž‰y¡q0/#*w… -}4_#LPEafŒ „v0l#£sWƒˆf{0>:LPGO;"[0 !-Žf{•¥ª R*#£sWYž$ƒˆf{"­/ !f{|Q#^”3d/+%% 

KL@C „Ió€ž4P GR8EN¹P4H:>-  ó€žJ  
  IiYraWwȏ®Høy;R  ó€žE†õHT>@C 
I̐«I/Ró€žD/Q,Œ¨ÃÂH37Rú«5|­9S>- JeslejVw ˆžUZdlsw]Œ¨;RŒ¨Uè;RE|­9SC0R8E4P,  Nesl ejVwꢂÿˆžUZdlsw];RŒ¨U±@C0RE² D6,WwfvZthbxtûÁ¥®H 37R *
#+*" D/REÝ2PSR-



 
                  





üÿýumdZoW_wȏ®ÙîIó€ žÎ› ÀUÊ0>ç½

ý





umdZoW_wȏ®ó€žI\vxgw]J,WwfvZthbxtH37RŠMCIȏ®ó€ž \vxgw]D/@>>M,¯.IHĀ]txlIÖ}HG@>-Ä©G5Pš˜ô‰IËäH30CJ 붰ÔD…Uí9S> ý-:4:G5P,8Ië¶J󀞬™H˜B0C,Žó€žIÃÞU² :C 3Q,FIO1Gz÷‚U~:CWwfvZthbxtûÁ5¥®9SR4HA0CJñKPSC0G4@ >-¯.J,8SLD™’IG4@>   £I¥ìï³ØU¸>HöË:,ó€žÎ›ÀUƒå, ç½;R8EHO@C,ȏ®z÷‚I Uã@>-\vxgw]9S>  ó€ž\r`cxI1?,

 
!*$'*!(&#'&'
 
 
"$#$$)*#'

*($&$"
 
 


A

O

O

7

N H

O

L-Tryptophan

RebH

H N

H N

O

N

StaG N H

N H

StaN

O HO

H N

O

N H

R1

N H

B

STA

C

REB

R1

(5 Staurosporine aglycon: R1, R2=H) (6 Rebeccamycin aglycon: R1=Cl, R2=O)

H N

O

O

H N

O

O

O-dTDP

O

HO

OH

HO

N H

Cl HO HO

NHCH3

1 Staurosporine

O-dTDP

OH

O

O-dTDP

StaJ HO

OH

O

O

O HO

O

H N

O-dTDP

StaI HO

OH

OH

H N

1'

NH2

O

7

RebM

Cl

6 Rebeccamycin aglycone

O

O-dTDP

StaK O

OH

RebG

O

NHCH3 8

O

OH

O

N O

H3CO

NH2

StaE O

N

StaMB 5'

O-dTDP

StaB

13

12

N O

StaMA

Holyrine B

O

N H

N

N O

NH2

OH TDP-Glucose

H N

StaN

HO

O

StaA HO

OH

N H

R1

(3 Chromopyrrolic acid: R1=H) (4 11,11'-Dichlorochromopyrrolic acid: R1=Cl)

N

NH2

O-P

OH D-Glucose

Cl

N H

N

HO

7 Holyrine A

O

N H

R1

HO

5 Staurosporine aglycone (K252c)

C

11'

O N H

HO

StaP/ StaC/ RebP RebC

RebO

B

O

O

7

N H

Cl

HO

R2 OH

11

NH4+ H2O

(Indolepyruvic acid: R1=H) (7-Chloroindolepyruvic acid: R1=Cl)

NH2

N H

N H

R1

OH

H N

O

HO

StaD/ RebD

O

StaO

NH2

H N

H N

O OH

OH

O-dTDP OH

OH TDP-Glucose

HO

N Cl

O

HO

HO OH

OH 9

13

N H

Cl

N

O

Cl 1'

HO

OH OCH3

2 Rebeccamycin

$
%(  #) A
  B

 '"&!*

$'$"#"#

$"#"!$ 
"%$ "



$"'!$ !
 #

"
$"#! "$"
 
EÏ|·¥R¤Â~¶ˆ¼ž-R±+?Æ6(:P;PE¯°­R ˆ’6(( R±+?ܺÕE„‘§ÌR«’6+ *&0::IeXTRaBb±}˜šÈ4uµ12=?%0=#ž3|Ôm‰4¸†§@pÉ (/!;¸†§4±²)=z}®9ˆ­352940=æê3ŒÜ3±²3˜y(+z} ®@º(/=¯3Ϧ0º(+z}®5¢Œá0x8/”;>+Ìz}®0=°ƒ*4¬–3. /5BQMCk0