78183-56-9Relevant articles and documents
Efficient (3S)-acetoin and (2S, 3S)-2, 3-butanediol production from meso-2, 3-butanediol using whole-cell biocatalysis
He, Yuanzhi,Chen, Feixue,Sun, Meijing,Gao, Huifang,Guo, Zewang,Lin, Hui,Chen, Jiebo,Jin, Wensong,Yang, Yunlong,Zhang, Liaoyuan,Yuan, Jun
, (2018/03/27)
(3S)-Acetoin and (2S, 3S)-2, 3-butanediol are important platform chemicals widely applied in the asymmetric synthesis of valuable chiral chemicals. However, their production by fermentative methods is difficult to perform. This study aimed to develop a whole-cell biocatalysis strategy for the production of (3S)-acetoin and (2S, 3S)-2, 3-butanediol from meso-2, 3-butanediol. First, E. coli co-expressing (2R, 3R)-2, 3-butanediol dehydrogenase, NADH oxidase and Vitreoscilla hemoglobin was developed for (3S)-acetoin production from meso-2, 3-butanediol. Maximum (3S)-acetoin concentration of 72.38 g/L with the stereoisomeric purity of 94.65% was achieved at 24 h under optimal conditions. Subsequently, we developed another biocatalyst co-expressing (2S, 3S)-2, 3-butanediol dehydrogenase and formate dehydrogenase for (2S, 3S)-2, 3-butanediol production from (3S)-acetoin. Synchronous catalysis together with two biocatalysts afforded 38.41 g/L of (2S, 3S)-butanediol with stereoisomeric purity of 98.03% from 40 g/L meso-2, 3-butanediol. These results exhibited the potential for (3S)-acetoin and (2S, 3S)-butanediol production from meso-2, 3-butanediol as a substrate via whole-cell biocatalysis.
Extended reaction scope of thiamine diphosphate dependent cyclohexane-1,2-dione hydrolase: From C-C bond cleavage to C-C bond ligation
Loschonsky, Sabrina,Wacker, Tobias,Waltzer, Simon,Giovannini, Pier Paolo,McLeish, Michael J.,Andrade, Susana L. A.,Müller, Michael
supporting information, p. 14402 - 14406 (2015/02/19)
ThDP-dependent cyclohexane-1,2-dione hydrolase (CDH) catalyzes the CC bond cleavage of cyclohexane-1,2-dione to 6-oxohexanoate, and the asymmetric benzoin condensation between benzaldehyde and pyruvate. One of the two reactivities of CDH was selectively knocked down by mutation experiments. CDH-H28A is much less able to catalyze the CC bond formation, while the ability for CC bond cleavage is still intact. The double variant CDH-H28A/N484A shows the opposite behavior and catalyzes the addition of pyruvate to cyclohexane-1,2-dione, resulting in the formation of a tertiary alcohol. Several acyloins of tertiary alcohols are formed with 54-94% enantiomeric excess. In addition to pyruvate, methyl pyruvate and butane-2,3-dione are alternative donor substrates for CC bond formation. Thus, the very rare aldehyde-ketone cross-benzoin reaction has been solved by design of an enzyme variant.
Elucidation of the enantioselective cyclohexane-1,2-dione hydrolase catalyzed formation of (S)-acetoin
Loschonsky, Sabrina,Waltzer, Simon,Brecht, Volker,Mueller, Michael
, p. 969 - 972 (2014/05/06)
Thiamine diphosphate (ThDP) dependent enzymes catalyze the formation of acetoin (3-hydroxybutan-2-one) through one of three different pathways: homocoupling of pyruvate, homocoupling of acetaldehyde, or cross-coupling of acetaldehyde (as acceptor) and pyruvate (as donor). The enantioselectivity of the resulting acetoin is highly dependent on the particular enzyme. We established that ThDP-dependent cyclohexane-1,2-dione hydrolase (CDH) is able to form (S)-acetoin with particularly high enantioselectivity (up to 95 % ee) by all three pathways. Mechanistic studies utilizing 13C-labeled substrates revealed an unprecedented non-acetolactate pathway for the homocoupling of pyruvate, which explains the high enantioselectivity in the CDH-catalyzed formation of (S)-acetoin. Differentiating hydrolases: Investigating thiamine diphosphate dependent cyclohexane-1,2-dione hydrolase (CDH) catalyzed homocoupling of 13C-labeled [1,2]-13C-pyruvate to (S)-[2,3]-13C-acetoin reveals a non-acetolactate pathway, which explains the high enantioselectivity of this reaction (up to 93 % ee). CDH also catalyzes the formation of (S)-acetoin by the cross-coupling of pyruvate and acetaldehyde and the homocoupling of acetaldehyde.
