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The two reactions compared are done so using a Tanimoto similarity score (for more information, please see the MACiE FAQ) for the bond changes only. The score maay range from 0 to 1 where 1 indicates that the two reactions are identical at the bond change level and 0 indicates that there are no bond changes in common.


Key

1.0-0.9 0.9-0.8 0.8-0.7 0.7-0.6 0.6-0.5 0.5-0.4 0.4-0.3 0.3-0.2 0.2-0.1 0.1-0.0 =0

Results for Comparison of M0137 and M0145

These two reactions have a combined similarity of 0.31


M0137

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Comparison

M0145

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EC 1.14.20.1
deacetoxycephalosporin-C synthase
Sub-Class EC 1.21.3.1
isopenicillin-N synthase

Image of oxygen

Image of penicilin N

Image of 2-oxoglutarate

right arrow

Image of carbon dioxide

Image of deacetoxycephalosporin C

Image of succinate

Image of water

oxygen
C00007
CHEBI:15379
penicilin N
C06564
CHEBI:58408
2-oxoglutarate
C00026
CHEBI:16810
carbon dioxide
C00011
CHEBI:16526
deacetoxycephalosporin C
C06565
CHEBI:58415
succinate
C00042
CHEBI:30031
water
C00001
CHEBI:15377
0.55

Image of delta(L-2-aminoadipyl)-L-cysteinyl-D-valine

Image of oxygen

Image of proton

right arrow

Image of water

Image of isopenicillin N

delta(L-2-aminoadipyl)-L-cysteinyl-D-valine
C05556
CHEBI:28496
oxygen
C00007
CHEBI:15379
proton
C00080
CHEBI:24636
2 water
C00001
CHEBI:15377
isopenicillin N
C05557
CHEBI:18165

Catalytic CATH Codes

Catalytic CATH Codes

2.60.120.330

Active Site



0.0333

Active Site



Catalytic Residues

There are no catalytic residues associated with this reaction mechanism
0

Catalytic Residues

Type Number Chain Location of Function
Phe 211 A Side Chain

Organic Cofactors

No Associated Organic Cofactors

Organic Cofactors

No Associated Organic Cofactors

Metal Cofactors

Type Het group Number Chain
iron FE2 1310 A

Metal Cofactors

Type Het group Number Chain
iron FE2 1336 A

Reaction occurs across 7 steps

0.38

Reaction occurs across 6 steps

Step 1
GIF of Reaction Step M0137.stg01

2-oxoglutarate initiates an electrophilic addition to dioxygen, which coordinates to the Fe(II) cofactor.
0 Step 1
GIF of Reaction Step M0145.stg01

Thiol of the substrate, delta(L-2-aminoadipyl)-L-cysteinyl-D-valine, coordinates to the iron cofactor in a nucleophilic substitution reaction, eliminating water.
Step 2
GIF of Reaction Step M0137.stg02

Carbon dioxide is eliminated from the intermediate to form a planar peroxo intermediate. Carbon dioxide is still coordinated to the Fe(II) cofactor.
0 Step 2
GIF of Reaction Step M0145.stg02

The iron cofactor initiates a homolytic addition to dioxygen, resulting in an iron bound dioxygen radical and iron in the Fe(III) oxidation step.
Step 3
GIF of Reaction Step M0137.stg03

Fe(II) initiates an elimination reaction by donating two electrons to the bound peroxo moiety, cleaving the peroxo bond and producing the succinate product and iron as a ferryl species.
0 Step 3
GIF of Reaction Step M0145.stg03

The iron coordinated sulfur eliminates a hydride from the bound intermediate, resulting in a peroxo species bound to the iron, and a single electron transfer back to the iron, regenerating the Fe(II) oxidation state.
Step 4
GIF of Reaction Step M0137.stg04

Penicillin binds, displacing the succinate and carbon dioxide as iron ligands. The oxo group deprotonates the CH3 of the penicillin, generating a alkyl radical and resulting in the donation of a single electron to Fe(IV).
0.2 Step 4
GIF of Reaction Step M0145.stg04

Iron is oxidised from Fe(II) to Fe(IV), forming an oxo group bound to the iron and causing the cleavage of the peroxo O-O bond, which deprotonates the amide in the intermediate, resulting in the formation of the four-membered beta-lactam ring bound to the iron cofactor.
Step 5
GIF of Reaction Step M0137.stg05

A colligation occurs between the alkyl radical and the sulfur of the five membered ring in the penicillin.
0.33 Step 5
GIF of Reaction Step M0145.stg05

The iron-bound sulfur attacks the intermediate in an internal nucleophilic substitution, resulting in the elimination of a hydride ion that attacks the peroxo group, forming a hydride and transferring two electrons back to the iron, regenerating the Fe(II) oxidation state and the isopenicillin N product.
Step 6
GIF of Reaction Step M0137.stg06

The C-S bond of the original five-mebered ring homolyses, producing the six-membered ring.
0 Step 6
GIF of Reaction Step M0145.stg06

Inferred return step in which the coordination sphere of the iron cofactor is regenerated by proton transfer from water.
Step 7
GIF of Reaction Step M0137.stg07

The carbon radical in the ring donates a single electron to the Fe(III) cofactor, which causes the bound hydroxide to deprotonate the C3 of the thiazolidine ring generating the final deacetoxycephalosporin C product.
N/A Step 7
No Step with this number present

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