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Abstract
Catalysis is one of the fundamental pillars of green chemistry, the design of chemical products and processes that reduce or
eliminate the use and generation of hazardous substances. The design and application of new catalysts and catalytic systems
are simultaneously achieving the dual goals of environmental protection and economic benefit.
No subject so pervades modern chemistry as that of catalysis. (Ron Breslow, Chemistry Today and Tomorrow: The Central,
Useful, and Creative Science)
Green chemistry, the design of chemical products and processes that reduce or eliminate the use and generation of hazardous
substances, is an overarching approach that is applicable to all aspects of chemistry. From feedstocks to solvents, to synthesis
and processing, green chemistry actively seeks ways to produce materials in a way that is more benign to human health and
the environment. The current emphasis on green chemistry reflects a shift away from the historic command-and-control
approach to environmental problems that mandated waste treatment and control and clean up through regulation, and toward
preventing pollution at its source. Rather than accepting waste generation and disposal as unavoidable, green chemistry
seeks new technologies that are cleaner and economically competitive. Utilizing green chemistry for pollution prevention
demonstrates the power and beauty of chemistry: through careful design, society can enjoy the products on which we depend
while benefiting the environment.
The economic benefits of green chemistry are central drivers in its advancement. Industry is adopting green chemistry
methodologies because they improve the corporate bottom line. A wide array of operating costs are decreased through the use
of green chemistry. When less waste is generated, environmental compliance costs go down. Treatment and disposal become
unnecessary when waste is eliminated. Decreased solvent usage and fewer processing steps lessen the material and energy
costs of manufacturing and increase material efficiency. The environmental, human health, and the economic advantages
realized through green chemistry are serving as a strong incentive to industry to adopt greener technologies.
Developing green chemistry methodologies is a challenge that may be viewed through the framework of the Twelve
Principles of Green Chemistry [1]. These principles identify catalysis as one of the most important tools for implementing
green chemistry. Catalysis offers numerous green chemistry benefits including lower energy requirements, catalytic versus
stoichiometric amounts of materials, increased selectivity, and decreased use of processing and separation agents, and al-
lows for the use of less toxic materials. Heterogeneous catalysis, in particular, addresses the goals of green chemistry by
providing the ease of separation of product and catalyst, thereby eliminating the need for separation through distillation or
extraction. In addition, environmentally benign catalysts such as clays and zeolites, may replace more hazardous catalysts
currently in use. This paper highlights a variety of ways in which catalysis may be used as a pollution prevention tool in green
0926-860X/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 1 ) 0 0 7 9 3 - 1
4 P.T. Anastas et al. / Applied Catalysis A: General 221 (2001) 313
chemistry reactions. The benefits to human health, environment, and the economic goals realized through the use of catalysis
in manufacturing and processing are illustrated by focusing on the catalyst design and catalyst applications. 2001 Elsevier
Science B.V. All rights reserved.
Keywords: Catalysis; Green chemistry; Environmental protection
1. Catalyst design alysts (Fig. 1) also permits the use of more environ-
mentally friendly feedstocks and reagents. Examples
The design of a catalyst strives to optimize fac- in this section illustrate the types of green chemistry
tors such as stability, turnover number, solubility, and benefits achieved through the appropriate design of a
ease of separation from the product. Changes in lig- catalyst.
and design or metal selection can provide significant The development of improved catalysts has facil-
improvements in selectivity, energy consumption, and itated the synthesis of a specific class of polycar-
solvent utilization. In some cases, design of better cat- bonates that are used as binders in ceramics. The
promise both water and energy conservation in the free radical mechanism has been proposed in which
laundry field. The versatility of TAMLTM activators the n-hexane is oriented within the molecular sieve
in catalyzing peroxide reactions promises further ap- such that the ends of the chain are in close proxim-
plications potentially in the critically important area ity to the radical-generating cobalt ions. The second
of water disinfection. The green chemistry benefits of protocol also employs air oxidation with a different
this chlorine-free oxidation using a non-toxic metal, molecular sieve catalyst containing iron(III) ions. Di-
mild reaction conditions, and a waste-free process are rect oxidation of cyclohexane to adipic acid with this
all due to thoughtful catalyst design. heterogeneous catalyst permits easy separation and re-
Advances in genetic engineering permit the cus- cycling of the catalyst, and avoids the use of typical
tomization of organisms to catalyze specific trans- corrosive and hazardous reagents. Both of these proce-
formations that are currently finding applications in dures eliminate the use of nitric acid found in conven-
numerous chemical processes. The work of Draths tional adipic acid syntheses, as well as the production
and Frost [4,5] exemplifies the use of biocatalysis in of the nitrous oxide byproduct.
organic synthesis. Using genetically engineered Kleb- Oxidation of alkanes and alkenes using t-butyl hy-
siella pneumoniae in a non-virulent strain of E. coli, droperoxide (TBHP) and O2 as oxidants has been
d-glucose may be converted to cis, cis-muconic acid, demonstrated by Fish and coworkers [7,8] using flu-
then reduced to adipic acid, a monomer in the manu- orous biphasic catalysis (FBC). Currently, the oxida-
facture of nylon-6,6 (Scheme 2). The traditional syn- tion of alkanes with TBHP occurs in a homogeneous
thesis of adipic acid uses benzene (a non-renewable, phase, resulting in a difficult separation of product
carcinogenic feedstock), employs high temperature and catalyst. With FBC, however, the oxidation prod-
and high pressure steps, and produces the greenhouse ucts and catalyst reside in separate phases, facilitating
gas nitrous oxide as a byproduct. The biocatalytic separation and recovery. The success of this reaction
approach features a renewable feedstock, uses mild depends upon the in situ generation of a precatalyst
reaction conditions, and emits no nitrous oxide. Simi- composed of a fluoroponytailed ligand and metal
lar genetic engineering using E. coli has also resulted complex (Fig. 3). The precatalyst initiates the forma-
in an effective catalyst in the synthesis of catechol, tion of radicals necessary for CH radical abstraction,
a chemical building block used to synthesize flavors ultimately yielding oxidation products. Combining a
such as vanillin. fluoroponytailed ligand with a metal catalyst yields
Two new catalytic routes to adipic acid have re- a precatalyst that is fluorous phase soluble, enabling
cently been reported by Thomas [6]. In one approach, simple separation of product and catalyst and easy
the terminal methyl groups of n-hexane are selectively recycle of the catalyst.
air oxidized to carboxylic acids using an aluminophos- In the nitration of aromatic compounds, solid
phate molecular sieve catalyst with cobalt(III) ions. A acid catalysts are a more environmentally benign
P.T. Anastas et al. / Applied Catalysis A: General 221 (2001) 313 7
2. Catalyst applications
Fig. 4. Calixarene bisphosphite ligand.
The application of catalysts is ubiquitous in the
chemical industry in areas ranging from pharmaceuti-
(Fig. 4) was found to give very high regioselectivity cals to polymers to petroleum processing. More than
(99.5%) in the conversion of 1-octene to n-nonanal. 90% of all industrial processes are based on catal-
Molecular modeling calculations on the catalyst sug- ysis [16]. The widespread utilization by industry of
gested that, by decreasing the steric requirements of catalytic processes reflects the economic and environ-
the ligand, the reaction rate could be increased without mental benefits achieved through catalysis.
compromising the regioselectivity. Subsequent exper- Ibuprofen is one of the most commonly used
iments confirmed this prediction; high regioselectivity over-the-counter pain relievers. The traditional syn-
was retained while the reaction time was cut in half and thesis requires six steps that use large volumes of sol-
milder reaction conditions were employed. The green vent, corrosive reagents, and stoichiometric quantities
chemistry benefits of this reaction include increased of materials. This protocol also exhibits poor atom
selectivity and decreased energy demands in the form economy, only 40% of the atoms in the starting ma-
of lower temperature and pressure requirements. terials are incorporated into the product. In contrast,
Bandgar and Kasture [14] and Bandgar et al. [15] the BHC synthesis [17] of ibuprofen is accomplished
have developed a protocol to catalytically remove in only three steps (Scheme 5). Catalytic amounts
carbonyl protecting groups under microwave radiation of reagents are used, and greater than 99% of the
and solvent-free conditions. Conventional cleavage HF catalyst is recycled and reused. Atom economy
and removal of thioacetals and thioketals frequently doubles to 80%, significantly reducing the amount
employ heavy metals such as mercury(II) chloride of waste generated. While there is concern that this
and selenium dioxide. Less toxic alternatives to improved synthesis of ibuprofen relies on anhydrous
mercury salts are desirable given the environmental hydrogen fluoride, it, however, does serve as both
problems associated with the use of mercury. Mi- catalyst and solvent to minimize aqueous and organic
crowaving the thioacetal or thioketal with a catalytic waste streams and maximize reaction efficiency.
amount of kaolinitic clay regenerates the carbonyl Another anti-inflammatory drug, Naproxen, can
compound in good yield (Scheme 4). A similar pro- be synthesized in high yield via a catalytic route
cedure has been developed for the deprotection of (Scheme 6) [18]. The final step in the synthetic se-
1,1-diacetates. Microwave activation of the diacetate quence employs a chiral transition metal catalyst
containing BINAP [2,2 -bis(diarylphospheno)-1,1 - macia and Upjohn [19] improved the manufacturing
binaphthyl] to produce the desired enantiomer in 97% process of bisnoraldehyde, a key intermediate in
yield. The high selectivity of the transition metal cata- the synthesis of progesterone and corticosteroids, by
lyst is attributed to steric factors that restrict rotation. switching from a heavy metal oxidant to a bleach and
Improved selectivity through catalysis minimizes or catalyst/co-factor system (Scheme 7). The revised
eliminates the need for product separation, reducing synthesis employs a genetically modified bacterium
the use of solvents and separation agents. that uses whole soya sterols, a renewable feedstock,
Catalytic methods can provide safer alternatives more efficiently than the previous process, increasing
to reagents commonly used in oxidation reactions, feedstock utilization from 15 to 100%. The new cat-
such as chromium, a suspected carcinogen. Phar- alytic features of the process reduce aqueous waste
by 79% and non-recoverable organic solvent waste by synthesis of cyclic imine sugars, which act as in-
89%. hibitors of glycoprocessing enzymes. An enzymatic
Traditional catalysts may be complemented by aldol condensation yields a mixture of azido sugars
enzymes that provide remarkable selectivity in or- that is subsequently hydrogenated under catalytic con-
ganic synthesis. Analogues of castanospermine, a ditions to cyclic imine sugars (Scheme 9). To prevent
potential AIDS drug, may be synthesized using the over-reduction of the azido sugar, the amino-carbonyl
enzyme catalyst subtilisin [20]. The regioselectiv- sugar intermediate was trapped as its hydrochloride
ity of the catalyst permits acylation exclusively at salt, yielding the desired cyclic imine rather than the
the C-1 hydroxyl group, leaving the remaining three fully hydrogenated iminocyclitol. Cyclic imines serve
secondary hydroxyl groups untouched (Scheme 8). as key intermediates in the synthesis of nitrogen het-
Typically, the synthesis of individual esters of cas- erocycles and iminocyclitols.
tanospermine requires protection and deprotection Eli Lilly and Company used an interdisciplinary
of the neighboring hydroxyl groups. Enzymatic syn- approach in redesigning the synthesis of an anticon-
thesis of castanospermine derivatives permits simple vulsant drug candidate [22]. In one key step, a biocat-
isolation and purification of the product, recovery and alyst was employed to selectively reduce the starting
reuse of unreacted starting material, and elimination ketone to the optically pure alcohol (Scheme 10).
of protection/deprotection steps. The yeast chosen to effect this transformation, Z.
Wong and coworkers [21] extensively use chemo- rouxii, was deactivated with increasing organic con-
enzymatic methods to synthesize a variety of bio- centration, necessitating the design of a three-phase
logically important compounds. One example is the system to prevent build-up of the product. Additional
selectivity for waste minimization are manifested in recombinant plant systems or by microbial fermen-
this approach. tation in aqueous media from renewable resources.
Ionic liquids are also gaining acceptance as alter- Gross and coworkers [28] have focused on producing
natives to traditional organic solvents. Ionic liquids PHAs with improved physico-mechanical properties
are non-volatile and non-flammable, eliminating the by integrating poly(ethylene glycol) (PEG) into the
hazards associated with volatile organic compounds culture media. PEG has proven effective in control-
(VOCs). In addition, the properties of ionic liquids ling the molecular weight and composition of PHAs.
may be tuned by varying the identities of the cations In addition to the biodegradability of the product,
and anions, thereby tailoring the solvent to a specific this approach offers additional environmental ben-
application. Kitazume and Zulfiqar [26] recently re- efits through its use of renewable feedstocks such
ported conducting the AzaDielsAlder reaction in as fructose, and its use of water as the reaction
ionic liquids (Scheme 14). This reaction is typically medium.
run in an organic solvent, using a corrosive Lewis acid
catalyst. The new procedure uses a microencapsulated
Lewis acid catalyst (scandium trifluoromethanesul- 3. Conclusion
fonate) that may be recovered and reused. The ionic
liquid is also reused following purification. This As has been illustrated in this paper, the utilization
one-pot synthesis demonstrates the potential of ionic of catalysis to achieve the goals of green chemistry
liquids as alternative solvents in traditional organic has met with tremendous success. Through the use of
reactions. catalytic systems, the dual goals of attaining environ-
Catalysts play a key role in the manufacture of mental and economic benefit simultaneously are being
biodegradable polymers. The Donlar Corporation realized in applications ranging from very small-scale
[27], for example, employs a catalytic process to fine chemical synthesis to commodity petrochemical
polymerize thermal polyaspartic acid (TPA). Lower processes. An additional benefit from the use of catal-
reaction temperatures and improved physical and per- ysis is that it enables the implementation of several
formance properties of the polymer are achieved using green chemistry goals ranging from the use of alterna-
the catalytic procedure. TPA, a non-toxic biodegrad- tive solvents such as SC-CO2 or water, to utilization
able polymer, is a viable replacement for polyacrylic of bio-based renewable feedstocks such as glucose, to
acid (PAC), which is not biodegradable. TPA has energy minimization.
proven effective in agricultural applications, where it The promise and the potential of catalysis are, how-
increases fertilizer and nutrient uptake of plants. TPA ever, even larger than their successes. Future devel-
is also useful as a corrosion and scale inhibitor in the opments in catalysis will propel the pursuit of green
water treatment industry. chemistry forward. The design of catalysts that both
Natural polyhydroxyalkanoates (PHAs) repre- activate otherwise inert starting materials as well as
sent another class of biodegradable polymers. These enhance reaction rates will reduce the current reliance
natural polyesters may be obtained directly from on reactive and toxic reagents. The continued move-
P.T. Anastas et al. / Applied Catalysis A: General 221 (2001) 313 13
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