KEGG   ENZYME: 2.3.1.111
Entry
EC 2.3.1.111                Enzyme                                 
Name
mycocerosate synthase;
mas (gene name);
mycocerosic acid synthase;
acyl-CoA:methylmalonyl-CoA C-acyltransferase (decarboxylating, oxoacyl- and enoyl-reducing);
long-chain acyl-CoA:methylmalonyl-CoA C-acyltransferase (mycocerosate-forming)
Class
Transferases;
Acyltransferases;
Transferring groups other than aminoacyl groups
Sysname
long-chain acyl-[mycocerosic acid synthase]:methylmalonyl-CoA C-acyltransferase (mycocerosate-forming)
Reaction(IUBMB)
(1) a long-chain acyl-[mycocerosic acid synthase] + 3 methylmalonyl-CoA + 6 NADPH + 6 H+ = a trimethylated-mycocerosoyl-[mycocerosate synthase] + 3 CoA + 3 CO2 + 6 NADP+ + 3 H2O;
(2) a long-chain acyl-[mycocerosic acid synthase] + 4 methylmalonyl-CoA + 8 NADPH + 8 H+ = a tetramethylated-mycocerosoyl-[mycocerosate synthase] + 4 CoA + 4 CO2 + 8 NADP+ + 4 H2O
Reaction(KEGG)
(other) R05189 R11450
Substrate
long-chain acyl-[mycocerosic acid synthase];
methylmalonyl-CoA [CPD:C02557];
NADPH [CPD:C00005];
H+ [CPD:C00080]
Product
trimethylated-mycocerosoyl-[mycocerosate synthase];
CoA [CPD:C00010];
CO2 [CPD:C00011];
NADP+ [CPD:C00006];
H2O [CPD:C00001];
tetramethylated-mycocerosoyl-[mycocerosate synthase]
Comment
The enzyme, characterized from mycobacteria, is loaded with a long-chain acyl moiety by EC 6.2.1.49, long-chain fatty acid adenylyltransferase FadD28, and elongates it by incorporation of three or four methylmalonyl (but not malonyl) residues, to form tri- or tetramethyl-branched fatty-acids, respectively, such as 2,4,6,8-tetramethyloctacosanoate (C32-mycocerosate). Since the enzyme lacks a thioesterase domain, the product remains bound and requires additional enzyme(s) for removal. Even though the enzyme can accept C6 to C20 substrates in vitro, it prefers to act on C14-C20 substrates in vivo.
History
EC 2.3.1.111 created 1989, modified 2016, modified 2017
Orthology
K11628  mycocerosic acid synthase
Genes
CPRACPter91_5287
MASSCR152_21455
MFBMFUL124B02_13660
GOHB932_3088
GTIFXF46_12120
MTURv2940c(mas)
MTVRVBD_2940c
MTCMT3010(mas-2)
MRAMRA_2966(mas)
MTFTBFG_12954
MTBTBMG_01032
MTKTBSG_01040
MTZTBXG_001020
MTGMRGA327_18070
MTECCDC5079_2700
MTURCFBS_3098(mas)
MTLCCDC5180_2664
MTOMTCTRI2_2997(mas)
MTDUDA_2940c(mas)
MTNERDMAN_3222(mas)
MTJJ112_15735
MTUBMT7199_2974
MTUEJ114_15700
MTXM943_15160
MTULTBHG_02870
MTUTHKBT1_3086(mas)
MTUUHKBT2_3091(mas)
MTQHKBS1_3093(mas)
MBOBQ2027_MB2965C(mas)
MBBBCG_2962c(mas)
MBTJTY_2957(mas)
MBMBCGMEX_2957c(mas)
MBKK60_030450
MBXBCGT_2778
MAFMAF_29450(mas)
MMICRN08_3240
MCEMCAN_29621(mas)
MCQBN44_60417(mas)
MCVBN43_40648(mas)
MCXBN42_40938(mas)
MCZBN45_51352(mas)
MLEML0139(mas)
MLBMLBr00139(mas)
MULMUL_2010(mas)
MMIMMAR_1767(mas)
MMAEMMARE11_16870(mas)
MLIMULP_01923(mas)
MKNMKAN_23980
MHADB586_03330
MSHGMSG_01621(mas)
MFJMFLOJ_16850(mas)
MSIMMSIM_07840(mas)
MPAGC0J29_10270
MGORH0P51_01940
MBAIMB901379_01582(mas)
MPSEMPSD_40670(mas)
MSHOMSHO_54730(mas)
MGAUMGALJ_49480(mas)
MLJMLAC_28780(mas)
MSHJMSHI_07270(mas)
MMAMK3U93_07795
MHOLK3U96_18775
MSPGF6B93_07120
MOTLTS72_16020
MLMMLPF_0168(mas)
NWLNWFMUON74_34950
SRTSrot_0318
SGMGCM10017557_82810
ROLCA51_49670(mas_2)
 » show all
Reference
1  [PMID:3880746]
  Authors
Rainwater DL, Kolattukudy PE.
  Title
Fatty acid biosynthesis in Mycobacterium tuberculosis var. bovis Bacillus Calmette-Guerin. Purification and characterization of a novel fatty acid synthase, mycocerosic acid synthase, which elongates n-fatty acyl-CoA with methylmalonyl-CoA.
  Journal
J Biol Chem 260:616-23 (1985)
  Sequence
Reference
2  [PMID:1527058]
  Authors
Mathur M, Kolattukudy PE
  Title
Molecular cloning and sequencing of the gene for mycocerosic acid synthase, a novel fatty acid elongating multifunctional enzyme, from Mycobacterium tuberculosis var. bovis Bacillus Calmette-Guerin.
  Journal
J Biol Chem 267:19388-95 (1992)
  Sequence
Reference
3  [PMID:15749014]
  Authors
Trivedi OA, Arora P, Vats A, Ansari MZ, Tickoo R, Sridharan V, Mohanty D, Gokhale RS
  Title
Dissecting the mechanism and assembly of a complex virulence mycobacterial lipid.
  Journal
Mol Cell 17:631-43 (2005)
DOI:10.1016/j.molcel.2005.02.009
Reference
4  [PMID:24831705]
  Authors
Menendez-Bravo S, Comba S, Sabatini M, Arabolaza A, Gramajo H
  Title
Expanding the chemical diversity of natural esters by engineering a polyketide-derived pathway into Escherichia coli.
  Journal
Metab Eng 24:97-106 (2014)
DOI:10.1016/j.ymben.2014.05.002
Other DBs
ExplorEnz - The Enzyme Database: 2.3.1.111
IUBMB Enzyme Nomenclature: 2.3.1.111
ExPASy - ENZYME nomenclature database: 2.3.1.111
BRENDA, the Enzyme Database: 2.3.1.111
CAS: 95229-19-9

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