ID 2.3.1.328 DE branched-chain 2-oxoacid:malonyl-[acyl-carrier protein] acyltransferase. CA N(6)-[(R)-lipoyl]-L-lysyl-[lipoyl-carrier protein] + 4-methyl-2- CA oxopentanoate + malonyl-[ACP] + 2 H(+) = 5-methyl-3-oxohexanoyl-[ACP] + CA N(6)-[(R)-dihydrolipoyl]-L-lysyl-[lipoyl-carrier protein] + 2 CO2. CC -!- The enzyme, characterized from an environmental DNA sample and CC expressed in Paraburkholderia graminis, is a complex enzyme whose CC purpose is to divert branched-chain 2-oxo acids to production of CC branched-chain N-acyl amino acids by producing branched 3-oxoacyl- CC [ACP] molecules. CC -!- NasB accepts branched-chain 2-oxoacids such as 4-methyl-2- CC oxopentanoate, and catalyzes a decarboxylative transfer to a thiamine CC diphosphate cofactor, followed by a transfer to a lipoyl cofactor, CC and finally a second decarboxylative transfer to the malonyl-[ACP] CC acceptor. CC -!- The products, such as 5-methyl-3-oxohexanoyl-[ACP], can be extended CC by the fatty acid synthase system to form branched long-chain fatty- CC acyl-[ACP] molecules, which serve as substrates for EC 2.3.1.327. CC -!- During the reaction the lipoyl cofactor is reduced to dihydrolipoyl, CC which must be oxidized back to lipoyl by an unknown enzyme. //