ID 2.3.1.292 DE (phenol)carboxyphthiodiolenone synthase. CA (1) icosanoyl-[(phenol)carboxyphthiodiolenone synthase] + 2 (S)- CA methylmalonyl-CoA + 3 malonyl-CoA + 5 NADPH + 10 H(+) = C32- CA carboxyphthiodiolenone-[(phenol)carboxyphthiodiolenone synthase] + 5 CO2 CA + 5 NADP(+) + 5 CoA + 2 H2O. CA (2) docosanoyl-[(phenol)carboxyphthiodiolenone synthase] + 2 (S)- CA methylmalonyl-CoA + 3 malonyl-CoA + 5 NADPH + 10 H(+) = C34- CA carboxyphthiodiolenone-[(phenol)carboxyphthiodiolenone synthase] + 5 CO2 CA + 5 NADP(+) + 5 CoA + 2 H2O. CA (3) 19-(4-hydroxyphenyl)nonadecanoyl-[(phenol)carboxyphthiodiolenone CA synthase] + 2 (S)-methylmalonyl-CoA + 3 malonyl-CoA + 5 NADPH + 10 H(+) = CA C37-(phenol)carboxyphthiodiolenone-[(phenol)carboxyphthiodiolenone CA synthase] + 5 CO2 + 5 NADP(+) + 5 CoA + 2 H2O. CA (4) 17-(4-hydroxyphenyl)heptadecanoyl-[(phenol)carboxyphthiodiolenone CA synthase] + 2 (S)-methylmalonyl-CoA + 3 malonyl-CoA + 5 NADPH + 10 H(+) = CA C35-(phenol)carboxyphthiodiolenone-[(phenol)carboxyphthiodiolenone CA synthase] + 5 CO2 + 5 NADP(+) + 5 CoA + 2 H2O. CC -!- The enzyme, which is a complex of five polyketide synthase proteins, CC is involved in the synthesis of the lipid core common to phthiocerols CC and phenolphthiocerols. CC -!- The first protein, PpsA, can accept either a C18 or C20 long-chain CC fatty acyl, or a (4-hydroxyphenyl)-C17 or C19 fatty acyl. CC -!- The substrates must first be adenylated by EC 6.2.1.59, which also CC loads them onto PpsA. CC -!- PpsA then extends them using a malonyl-CoA extender unit. CC -!- The PpsB protein adds the next malonyl-CoA extender unit. CC -!- The absence of a dehydratase and an enoyl reductase domains in the CC PpsA and PpsB modules results in the formation of the diol portion of CC the phthiocerol moiety. CC -!- PpsC adds a third malonyl unit (releasing a water molecule due to its CC dehydratase domain), PpsD adds an (R)-methylmalonyl unit, releasing a CC water molecule, and PpsE adds a second (R)-methylmalonyl unit, CC without releasing a water molecule. CC -!- The incorporation of the methylmalonyl units results in formation of CC two branched methyl groups in the elongated product. CC -!- The enzyme does not contain a thioesterase domain, and release of the CC products requires the tesA-encoded type II thioesterase. DR Q7TXM0, PPSA_MYCBO ; P9WQE6, PPSA_MYCTO ; P9WQE7, PPSA_MYCTU ; DR Q7TXL9, PPSB_MYCBO ; P9WQE4, PPSB_MYCTO ; P9WQE5, PPSB_MYCTU ; DR Q7TXL8, PPSC_MYCBO ; P96202, PPSC_MYCTU ; Q7TXL7, PPSD_MYCBO ; DR P9WQE2, PPSD_MYCTO ; P9WQE3, PPSD_MYCTU ; Q7TXL6, PPSE_MYCBO ; DR P9WQE0, PPSE_MYCTO ; P9WQE1, PPSE_MYCTU ; //