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Regio‐ and Stereoselective Aliphatic–Aromatic Cross‐Benzoin Reaction: Enzymatic Divergent Catalysis
Author(s) -
Beigi Maryam,
Gauchenova Ekaterina,
Walter Lydia,
Waltzer Simon,
Bonina Fabrizio,
Stillger Thomas,
Rother Dörte,
Pohl Martina,
Müller Michael
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201602084
Subject(s) - chemistry , pseudomonas fluorescens , benzoin , stereoselectivity , regioselectivity , stereochemistry , enantiomeric excess , catalysis , enzyme , enantiomer , organic chemistry , enantioselective synthesis , bacteria , genetics , biology
The catalytic asymmetric synthesis of chiral 2‐hydroxy ketones by using different thiamine diphosphate dependent enzymes, namely benzaldehyde lyase from Pseudomonas fluorescens ( Pf BAL), a variant of benzoylformate decarboxylase from Pseudomonas putida ( Pp BFD‐L461A), branched‐chain 2‐keto acid decarboxylase from Lactococcus lactis ( Ll KdcA) and a variant of pyruvate decarboxylase from Acetobacter pasteurianus ( Ap PDC‐E469G), was studied. Starting with the same set of substrates, substituted benzaldehydes in combination with different aliphatic aldehydes, Pf BAL and Pp BFD‐L461A selectively deliver the ( R )‐ and ( S )‐2‐hydroxy‐propiophenone derivatives, respectively. The ( R )‐ and ( S )‐phenylacetylcarbinol (1‐hydroxy‐1‐phenylacetone) derivatives are accessible in a similar way using Ll KdcA and Ap PDC‐E469G, respectively. In many cases excellent stereochemical purities (>98 % enantiomeric excess) could be achieved. Hence, the regio‐ and stereochemistry of the product in the asymmetric aliphatic–aromatic cross‐benzoin reaction can be controlled solely by choice of the appropriate enzyme or enzyme variant.