ENTRY ko01051 Pathway NAME Biosynthesis of ansamycins CLASS Metabolism; Metabolism of terpenoids and polyketides PATHWAY_MAP ko01051 Biosynthesis of ansamycins DRUG D02549 Rifamycin (USAN/INN) DBLINKS GO: 0033070 ORTHOLOGY K00615 E2.2.1.1, tktA, tktB; transketolase [EC:2.2.1.1] K15466 rifF, asm9; amide synthase K15467 rif14; 27-O-demethylrifamycin SV methyltransferase [EC:2.1.1.315] K15670 rifA; rifamycin polyketide synthase modules 1, 2 and 3 [EC:6.2.1.74] K15671 rifB; rifamycin polyketide synthase modules 4, 5 and 6 K15672 rifC_D; rifamycin polyketide synthase modules 7 and 8 K15673 rifE; rifamycin polyketide synthase modules 9 and 10 K16015 rifL, asm44; oxidoreductase [EC:1.1.1.-] K16016 rifK, asm24, asm43; 3-amino-5-hydroxybenzoate synthase [EC:4.2.1.144 2.6.1.-] K16017 rifM, asm45; AHBA synthesis associated protein K16018 rifN, asm22; kanosamine 6-kinase [EC:2.7.1.179] K16019 rifH; 3,4-Dideoxy-4-amino-D-arabino-heptulosonate 7-phosphate synthase K16020 rifG, asm47; 5-deoxy-5-amino-3-dehydroquinate synthase K16021 rifJ, asm23; 5-deoxy-5-amino-3-dehydroquinate dehydratase K16022 rif19; flavoprotein hydroxylase K16023 rif20; acetyltransferase K16024 asm13; methoxymalonate biosynthesis protein K16025 asm14; methoxymalonate biosynthesis acyl carrier protein K16026 asm15; methoxymalonate biosynthesis protein K16027 asm16; methoxymalonate biosynthesis protein K16028 asm17; O-methyltransferase K16029 asmA; ansamitocin polyketide synthase A K16030 asmB; ansamitocin polyketide synthase B K16031 asmC; ansamitocin polyketide synthase C K16032 asmD; ansamitocin polyketide synthase D K16033 asm12; FADH2-dependent halogenase K16034 asm7; 20-O-methyltransferase K16035 asm21; 7-O-carbamoyltransferase [EC:2.1.3.-] K16036 asm19; 3-O-acyltransferase K16037 asm11; 4,5-epoxidase K16038 asm10; N-methyltransferase [EC:2.1.1.-] K16039 asm25; N-glycosyltransferase [EC:2.4.1.-] COMPOUND C00029 UDP-glucose C01848 Rifamycin B C12044 Rifamycin C12045 Ansamitocin P-3 C12106 AminoDAHP C12107 3-Amino-5-hydroxybenzoate C12108 5-Amino-5-deoxy-3-dehydroshikimate C12109 AminoDHQ C12176 Proansamycin X C12177 Proansamitocin C12210 UDP-3-ketoglucose C12211 UDP-kanosamine C12212 Kanosamine C12213 Kanosamine 6-phosphate C12214 Aminofructose 6-phosphate C12215 Iminoerythrose 4-phosphate C12246 Protorifamycin I C12247 Rifamycin W C14540 Rifamycin S C14721 34a-Deoxy-rifamycin W C14722 Rifamycin W-hemiacetal C14723 Rifamycin Z C14724 Demethyl-desacetyl-rifamycin S C14725 27-O-Demethyl-25-O-desacetylrifamycin SV C14727 27-O-Demethylrifamycin SV C20134 19-Chloroproansamitocin C20135 20-O-Methyl-19-chloroproansamitocin C20136 N-Demethyl-desepoxymaytansinol C20137 N-Demethyl-desepoxyansamitocin P-3 C20138 N-Demethylansamitocin P-3 C20139 Ansamitocinoside P-3 C20140 4''-O-Carbamoyl ansamitocinoside P-3 REFERENCE PMID:22193711 AUTHORS Kang Q, Shen Y, Bai L TITLE Biosynthesis of 3,5-AHBA-derived natural products. JOURNAL Nat Prod Rep 29:243-63 (2012) DOI:10.1039/c2np00019a REFERENCE PMID:21081954 AUTHORS Floss HG, Yu TW, Arakawa K TITLE The biosynthesis of 3-amino-5-hydroxybenzoic acid (AHBA), the precursor of mC7N units in ansamycin and mitomycin antibiotics: a review. JOURNAL J Antibiot (Tokyo) 64:35-44 (2011) DOI:10.1038/ja.2010.139 REFERENCE PMID:12207504 AUTHORS Guo J, Frost JW TITLE Kanosamine biosynthesis: a likely source of the aminoshikimate pathway's nitrogen atom. JOURNAL J Am Chem Soc 124:10642-3 (2002) DOI:10.1021/ja026628m REFERENCE PMID:17076505 AUTHORS Wenzel SC, Williamson RM, Grunanger C, Xu J, Gerth K, Martinez RA, Moss SJ, Carroll BJ, Grond S, Unkefer CJ, Muller R, Floss HG TITLE On the biosynthetic origin of methoxymalonyl-acyl carrier protein, the substrate for incorporation of "glycolate" units into ansamitocin and soraphen A. JOURNAL J Am Chem Soc 128:14325-36 (2006) DOI:10.1021/ja064408t REFERENCE PMID:11996558 AUTHORS Kato Y, Bai L, Xue Q, Revill WP, Yu TW, Floss HG TITLE Functional expression of genes involved in the biosynthesis of the novel polyketide chain extension unit, methoxymalonyl-acyl carrier protein, and engineered biosynthesis of 2-desmethyl-2-methoxy-6-deoxyerythronolide B. JOURNAL J Am Chem Soc 124:5268-9 (2002) DOI:10.1021/ja0127483 REFERENCE PMID:12060743 AUTHORS Yu TW, Bai L, Clade D, Hoffmann D, Toelzer S, Trinh KQ, Xu J, Moss SJ, Leistner E, Floss HG TITLE The biosynthetic gene cluster of the maytansinoid antitumor agent ansamitocin from Actinosynnema pretiosum. JOURNAL Proc Natl Acad Sci U S A 99:7968-73 (2002) DOI:10.1073/pnas.092697199 REFERENCE PMID:14624546 AUTHORS Spiteller P, Bai L, Shang G, Carroll BJ, Yu TW, Floss HG TITLE The post-polyketide synthase modification steps in the biosynthesis of the antitumor agent ansamitocin by Actinosynnema pretiosum. JOURNAL J Am Chem Soc 125:14236-7 (2003) DOI:10.1021/ja038166y REFERENCE PMID:19292483 AUTHORS Taft F, Brunjes M, Knobloch T, Floss HG, Kirschning A TITLE Timing of the Delta(10,12)-Delta(11,13) double bond migration during ansamitocin biosynthesis in Actinosynnema pretiosum. JOURNAL J Am Chem Soc 131:3812-3 (2009) DOI:10.1021/ja8088923 REFERENCE PMID:22195559 AUTHORS Li Y, Zhao P, Kang Q, Ma J, Bai L, Deng Z TITLE Dual carbamoylations on the polyketide and glycosyl moiety by asm21 result in extended ansamitocin biosynthesis. JOURNAL Chem Biol 18:1571-80 (2011) DOI:10.1016/j.chembiol.2011.11.007 REFERENCE PMID:21681880 AUTHORS Wu Y, Kang Q, Shang G, Spiteller P, Carroll B, Yu TW, Su W, Bai L, Floss HG TITLE N-methylation of the amide bond by methyltransferase asm10 in ansamitocin biosynthesis. JOURNAL Chembiochem 12:1759-66 (2011) DOI:10.1002/cbic.201100062 REFERENCE PMID:18721757 AUTHORS Zhao P, Bai L, Ma J, Zeng Y, Li L, Zhang Y, Lu C, Dai H, Wu Z, Li Y, Wu X, Chen G, Hao X, Shen Y, Deng Z, Floss HG TITLE Amide N-glycosylation by Asm25, an N-glycosyltransferase of ansamitocins. JOURNAL Chem Biol 15:863-74 (2008) DOI:10.1016/j.chembiol.2008.06.007 REFERENCE PMID:12207505 AUTHORS Arakawa K, Muller R, Mahmud T, Yu TW, Floss HG TITLE Characterization of the early stage aminoshikimate pathway in the formation of 3-amino-5-hydroxybenzoic acid: the RifN protein specifically converts kanosamine into kanosamine 6-phosphate. JOURNAL J Am Chem Soc 124:10644-5 (2002) DOI:10.1021/ja0206339 REFERENCE PMID:12888623 AUTHORS Watanabe K, Rude MA, Walsh CT, Khosla C TITLE Engineered biosynthesis of an ansamycin polyketide precursor in Escherichia coli. JOURNAL Proc Natl Acad Sci U S A 100:9774-8 (2003) DOI:10.1073/pnas.1632167100 REFERENCE PMID:15700959 AUTHORS Floss HG, Yu TW. TITLE Rifamycin-mode of action, resistance, and biosynthesis. JOURNAL Chem Rev 105:621-32 (2005) DOI:10.1021/cr030112j REFERENCE PMID:12623077 AUTHORS Xu J, Mahmud T, Floss HG TITLE Isolation and characterization of 27-O-demethylrifamycin SV methyltransferase provides new insights into the post-PKS modification steps during the biosynthesis of the antitubercular drug rifamycin B by Amycolatopsis mediterranei S699. JOURNAL Arch Biochem Biophys 411:277-88 (2003) DOI:10.1016/S0003-9861(03)00004-3 REFERENCE PMID:15791687 AUTHORS Xiong Y, Wu X, Mahmud T TITLE A homologue of the Mycobacterium tuberculosis PapA5 protein, rif-orf20, is an acetyltransferase involved in the biosynthesis of antitubercular drug rifamycin B by Amycolatopsis mediterranei S699. JOURNAL Chembiochem 6:834-7 (2005) DOI:10.1002/cbic.200400387 REFERENCE PMID:16079331 AUTHORS Xu J, Wan E, Kim CJ, Floss HG, Mahmud T TITLE Identification of tailoring genes involved in the modification of the polyketide backbone of rifamycin B by Amycolatopsis mediterranei S699. JOURNAL Microbiology 151:2515-28 (2005) DOI:10.1099/mic.0.28138-0 REL_PATHWAY ko00520 Amino sugar and nucleotide sugar metabolism ///