ID   2.3.1.292
DE   (phenol)carboxyphthiodiolenone synthase.
CA   (1) 2 (S)-methylmalonyl-CoA + 10 H(+) + icosanoyl-
CA   [(phenol)carboxyphthiodiolenone synthase] + 3 malonyl-CoA + 5 NADPH =
CA   C32-carboxyphthiodiolenone-[(phenol)carboxyphthiodiolenone synthase] +
CA   5 CO2 + 5 CoA + 2 H2O + 5 NADP(+).
CA   (2) 2 (S)-methylmalonyl-CoA + docosanoyl-[(phenol)carboxyphthiodiolenone
CA   synthase] + 10 H(+) + 3 malonyl-CoA + 5 NADPH = C34-
CA   carboxyphthiodiolenone-[(phenol)carboxyphthiodiolenone synthase] + 5 CO2
CA   + 5 CoA + 2 H2O + 5 NADP(+).
CA   (3) 2 (S)-methylmalonyl-CoA + 19-(4-hydroxyphenyl)nonadecanoyl-
CA   [(phenol)carboxyphthiodiolenone synthase] + 10 H(+) + 3 malonyl-CoA +
CA   5 NADPH = C37-(phenol)carboxyphthiodiolenone-
CA   [(phenol)carboxyphthiodiolenone synthase] + 5 CO2 + 5 CoA + 2 H2O +
CA   5 NADP(+).
CA   (4) 2 (S)-methylmalonyl-CoA + 17-(4-hydroxyphenyl)heptadecanoyl-
CA   [(phenol)carboxyphthiodiolenone synthase] + 10 H(+) + 3 malonyl-CoA +
CA   5 NADPH = C35-(phenol)carboxyphthiodiolenone-
CA   [(phenol)carboxyphthiodiolenone synthase] + 5 CO2 + 5 CoA + 2 H2O +
CA   5 NADP(+).
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 ;
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