Scalable Green Approach Toward Fragrant Acetates

The advantageous properties of ethylene glycol diacetate (EGDA) qualify it as a useful substitute for glycerol triacetate (GTA) for various green applications. We scrutinised the lipase-mediated acetylation of structurally diverse alcohols in neat EGDA furnishing the range of naturally occurring fragrant acetates. We found that such enzymatic system exhibits high reactivity and selectivity towards activated (homo) allylic and non-activated primary/secondary alcohols. This feature was utilised in the scalable multigram synthesis of fragrant (Z)-hex-3-en-1-yl acetate in 70% yield. In addition, the Lipozyme 435/EGDA system was also found to be applicable for the chemo-selective acetylation of (hydroxyalkyl) phenols as well as for the kinetic resolution of chiral secondary alcohols. Lastly, its discrimination power was demonstrated in competitive experiments of equimolar mixtures of two isomeric alcohols. This enabled the practical synthesis of 1-pentyl acetate isolated as a single product in 68% yield from the equimolar mixture of 1-pentanol and 3-pentanol.

[1]  S. Riva,et al.  Natural flavor ester synthesis catalyzed by lipases , 2020 .

[2]  F. Molinari,et al.  Continuous preparation of flavour‐active acetate esters by direct biocatalytic esterification , 2019, Flavour and Fragrance Journal.

[3]  Kalaiarasi,et al.  Acetylation of Alcohols, Amines, Phenols, Thiols under Catalyst and Solvent-Free Conditions , 2019, Chemistry.

[4]  F. Molinari,et al.  Efficient Enzymatic Preparation of Flavor Esters in Water. , 2019, Journal of agricultural and food chemistry.

[5]  J. Gómez,et al.  Kinetic modelling and kinetic parameters calculation in the lipase-catalysed synthesis of geranyl acetate , 2018, Chemical Engineering Research and Design.

[6]  Raquel A. C. Leão,et al.  Continuous-Flow Chemo and Enzymatic Synthesis of Monoterpenic Esters with Integrated Purification , 2018, Molecular Catalysis.

[7]  M. Carević,et al.  Highly efficient enzymatic acetylation of flavonoids: Development of solvent-free process and kinetic evaluation , 2017 .

[8]  D. Oliveira,et al.  A review on enzymatic synthesis of aromatic esters used as flavor ingredients for food, cosmetics and pharmaceuticals industries , 2017 .

[9]  Á. Szécsényi,et al.  Neat lipase-catalysed kinetic resolution of racemic 1-phenylethanol and a straightforward modelling of the reaction , 2017 .

[10]  S. Hamdan,et al.  Deracemization of Secondary Alcohols by using a Single Alcohol Dehydrogenase , 2016 .

[11]  Prerana D. Tomke,et al.  Ultrasound assisted lipase catalyzed synthesis of cinnamyl acetate via transesterification reaction in a solvent free medium. , 2015, Ultrasonics sonochemistry.

[12]  E. García‐Verdugo,et al.  Green bioprocesses in sponge-like ionic liquids , 2015 .

[13]  B. Bhanage,et al.  Synthesis of lipase nano-bio-conjugates as an efficient biocatalyst: characterization and activity–stability studies with potential biocatalytic applications , 2015 .

[14]  W. Qi,et al.  Lipase immobilized on novel ceramic supporter with Ni activation for efficient cinnamyl acetate synthesis , 2014 .

[15]  B. Bhanage,et al.  Synthesis of geranyl acetate in non-aqueous media using immobilized Pseudomonas cepacia lipase on biodegradable polymer film: Kinetic modelling and chain length effect study , 2014 .

[16]  K. Kulangiappar,et al.  Nuclear Versus Side-Chain Bromination of 4-Methoxy Toluene by an Electrochemical Method , 2014 .

[17]  Héctor García-Marín,et al.  Glycerol based solvents: synthesis, properties and applications , 2014 .

[18]  Ashok Pandey,et al.  Advances in lipase-catalyzed esterification reactions. , 2013, Biotechnology advances.

[19]  Yuan Liu,et al.  Cephalosporolide B serving as a versatile synthetic precursor: asymmetric biomimetic total syntheses of cephalosporolides C, E, F, G, and (4-OMe-)G. , 2013, Organic letters.

[20]  Kaoru Nakamura,et al.  Asymmetric synthesis of enantiomerically pure zingerols by lipase-catalyzed transesterification and efficient synthesis of their analogues , 2013 .

[21]  B. Bhanage,et al.  Lipase: A potential biocatalyst for the synthesis of valuable flavour and fragrance ester compounds , 2013 .

[22]  S. Dhakate,et al.  Geranyl acetate synthesis catalyzed by Thermomyces lanuginosus lipase immobilized on electrospun polyacrylonitrile nanofiber membrane , 2013 .

[23]  T. Miyazawa,et al.  Chemoselective acylation of (hydroxyalkyl)phenols catalyzed by Candida antarctica lipase B , 2012, Biotechnology Letters.

[24]  P. Lozano,et al.  A clean enzymatic process for producing flavour esters by direct esterification in switchable ionic liquid/solid phases , 2012 .

[25]  A. Wolfson,et al.  A sustainable one-pot synthesis of cinnamyl acetate in triacetin , 2012 .

[26]  W. Qi,et al.  Cinnamyl acetate synthesis by lipase‐catalyzed transesterification in a solvent‐free system , 2012, Biotechnology and applied biochemistry.

[27]  G. Yadav,et al.  Lipase catalyzed synthesis of cinnamyl acetate via transesterification in non-aqueous medium , 2012 .

[28]  Zoltán Boros,et al.  Novel Sol-Gel Lipases by Designed Bioimprinting for Continuous-Flow Kinetic Resolutions , 2011 .

[29]  P. Macheroux,et al.  A Stereoselective Inverting sec-Alkylsulfatase for the Deracemization of sec-Alcohols , 2011, Organic letters.

[30]  V. Cadierno,et al.  Glycerol and derived solvents: new sustainable reaction media for organic synthesis. , 2011, Chemical communications.

[31]  A. Boffi,et al.  The Heck Reaction of Allylic Alcohols Catalyzed by Palladium Nanoparticles in Water: Chemoenzymatic Synthesis of (R)‐(−)‐Rhododendrol , 2011 .

[32]  E. Macedo,et al.  Geranyl acetate synthesis in a packed-bed reactor catalyzed by novozym in supercritical carbon dioxide and in supercritical ethane , 2011 .

[33]  B. Koczka,et al.  Fine-tuning the second generation sol–gel lipase immobilization with ternary alkoxysilane precursor systems , 2011 .

[34]  F. Péter,et al.  Preparation and properties of xerogels obtained by ionic liquid incorporation during the immobilization of lipase by the sol-gel method , 2010 .

[35]  F. Jérôme,et al.  Glycerol as a sustainable solvent for green chemistry , 2010 .

[36]  K. Engel,et al.  Preparation of passion fruit-typical 2-alkyl ester enantiomers via lipase-catalyzed kinetic resolution. , 2010, Journal of agricultural and food chemistry.

[37]  A. Wolfson,et al.  Glycerol triacetate as solvent and acyl donor in the production of isoamyl acetate with Candida antarctica lipase B , 2010, Bioprocess and biosystems engineering.

[38]  X. Fernandez,et al.  Reaction design for evaluation of the substrate range of hydrolases , 2008 .

[39]  A. Wolfson,et al.  Lipase catalyse glycerolysis for kinetic resolution of racemates , 2007, Bioprocess and biosystems engineering.

[40]  H. Yanagishita,et al.  [Optical resolution of 2-alkanol by lipase-catalyzed acetylation with vinyl acetate in packed-bed reactor with recycling system]. , 2007, Journal of oleo science.

[41]  J. Sánchez-montero,et al.  Characterization and catalytic properties of a new crude lipase from C. rugosa , 2006 .

[42]  D. Barahona,et al.  Effect of water activity on the lipase catalyzed esterification of geraniol in ionic liquid [bmim]PF6. , 2006, Biotechnology and bioengineering.

[43]  J. Yadav,et al.  Reaction of Orthoesters with Alcohols in the Presence of Acidic Catalysts: A Study. , 2005 .

[44]  S. Barreiros,et al.  Effect of zeolites on lipase catalyzed esterification in nonaqueous media , 2005 .

[45]  T. Punniyamurthy,et al.  Cobalt(II)-catalyzed direct acetylation of alcohols with acetic acid , 2005 .

[46]  C. Triantaphylidès,et al.  Lipase catalyzed formation of flavour esters , 1988, Biotechnology Letters.

[47]  T. Nishio,et al.  Terpene alcohol ester synthesis by polyethylene glycol-modified lipase in benzene , 1987, Biotechnology Letters.

[48]  C. Shieh,et al.  Studies on the optimized lipase-catalyzed biosynthesis of cis-3-hexen-1-yl acetate in n-hexane , 2003 .

[49]  S. Shibuya,et al.  Resolution of Racemic Rhododendrol by Lipase-Catalyzed Enantioselective Acetylation , 2003 .

[50]  P. Czermak,et al.  Lipase-catalyzed synthesis of geranyl acetate in n-hexane with membrane-mediated water removal. , 2001, Biotechnology and bioengineering.

[51]  Shih-yow Huang,et al.  Kinetic study on the esterification of geraniol and acetic acid in organic solvents using surfactant‐coated lipase , 1999 .

[52]  Bourg-Garros,et al.  Large-scale preparation of (Z)-3-hexen-1-yl acetate using candida antarctica-immobilized lipase in hexane , 1998, Biotechnology and bioengineering.

[53]  A. Pavia,et al.  Optimization of lipase-catalyzed synthesis of (z)-3-hexen-1-yl acetate by direct esterification in hexane and a solvent-free medium , 1998 .

[54]  C. Akoh,et al.  Enzymatic synthesis of geranyl acetate by transesterification with acetic anhydride as acyl donor , 1996 .

[55]  C. Akoh,et al.  Lipase-catalyzed synthesis of primary terpenyl acetates by transesterification: study of reaction parameters , 1994 .

[56]  C. Akoh,et al.  Enzymatic synthesis of geranyl acetate inn-hexane withCandida antarctica lipases , 1994 .

[57]  D. Combes,et al.  Kinetics of geranyl acetate synthesis by lipase-catalysed transesterification in n-hexane , 1992 .

[58]  Aviva Rappaport,et al.  A rule to predict which enantiomer of a secondary alcohol reacts faster in reactions catalyzed by cholesterol esterase, lipase from Pseudomonas cepacia, and lipase from Candida rugosa , 1991 .

[59]  R. Zingaro,et al.  Reactions of the Silver Salts of Carboxylic Acids with Iodine in the Presence of Some Tertiary Amines , 1949 .