TY - JOUR
T1 - Pouteria sapota hydroxynitrile lyase catalyzed synthesis of optically active cyanohydrins from ortho-substituted benzaldehydes
AU - Martínez-Casares, R. Marlen
AU - Pérez, Herminia I.
AU - Manjarrez, Norberto
AU - Solís-Oba, Myrna
AU - Ortega, Lucia
AU - Solís, Aida
N1 - Publisher Copyright:
© 2020 Elsevier B.V.
PY - 2020/10/1
Y1 - 2020/10/1
N2 - Chiral cyanohydrins are important building blocks in the preparation of pharmaceuticals and agrochemicals. The synthesis of optically active o-substituted mandelonitriles was carried out in a biphasic system, using the defatted meal of Pouteria sapota seeds as (R)-hydroxynitrile lyase (PsHNL) source to biocatalyze the enantioselective addition of HCN to the sterically hindered o-chloro, o-bromo, o-fluoro, o-nitro, o-methyl, and 2,4-dichlobenzaldehydes, that are poor substrates for other HNLs. The enantiomeric excess (ee) of the cyanohydrins obtained was from 98 to 100 %, except in the case of o-nitromandelonitrile (82 % ee), the conversion was from 56 % to 100 %, at the optimum conditions of 2 mL diisopropyl ether (i-pr2O), 37.5 %, of aqueous phase and ratio 60 mg/0.5 mmol of PsHNL meal/aldehyde. The relationship between molecular descriptors and bioconversion of the o-substituted benzaldehydes was analyzed using Person´s correlation (r ≤ 0.8) and path analysis, the molecular descriptors that had a highest influence over the conversion were Total size indexes (T) weighted by atomic van der Waals volume (Tv), atomic polarizability (Tp), atomic Sanderson electronegativity (Te) and unweighted (Tu). The P. sapota seed is an inexpensive source of HNL, that was able to biocatalyze the conversion of sterically hindered benzaldehydes to the corresponding enantiopure cyanohydrins.
AB - Chiral cyanohydrins are important building blocks in the preparation of pharmaceuticals and agrochemicals. The synthesis of optically active o-substituted mandelonitriles was carried out in a biphasic system, using the defatted meal of Pouteria sapota seeds as (R)-hydroxynitrile lyase (PsHNL) source to biocatalyze the enantioselective addition of HCN to the sterically hindered o-chloro, o-bromo, o-fluoro, o-nitro, o-methyl, and 2,4-dichlobenzaldehydes, that are poor substrates for other HNLs. The enantiomeric excess (ee) of the cyanohydrins obtained was from 98 to 100 %, except in the case of o-nitromandelonitrile (82 % ee), the conversion was from 56 % to 100 %, at the optimum conditions of 2 mL diisopropyl ether (i-pr2O), 37.5 %, of aqueous phase and ratio 60 mg/0.5 mmol of PsHNL meal/aldehyde. The relationship between molecular descriptors and bioconversion of the o-substituted benzaldehydes was analyzed using Person´s correlation (r ≤ 0.8) and path analysis, the molecular descriptors that had a highest influence over the conversion were Total size indexes (T) weighted by atomic van der Waals volume (Tv), atomic polarizability (Tp), atomic Sanderson electronegativity (Te) and unweighted (Tu). The P. sapota seed is an inexpensive source of HNL, that was able to biocatalyze the conversion of sterically hindered benzaldehydes to the corresponding enantiopure cyanohydrins.
KW - Cyanohydrin
KW - Hydroxynitrile lyase
KW - Molecular descriptor
KW - Ortho-benzaldehydes
KW - Pouteria sapota
UR - http://www.scopus.com/inward/record.url?scp=85085739552&partnerID=8YFLogxK
U2 - 10.1016/j.indcrop.2020.112606
DO - 10.1016/j.indcrop.2020.112606
M3 - Artículo
SN - 0926-6690
VL - 153
JO - Industrial Crops and Products
JF - Industrial Crops and Products
M1 - 112606
ER -