Solvents are a key area of focus for organic chemists looking to improve the
greenness of their processes as they are usually the largest mass input of a
synthetic process or transformation.
A comprehensive tool for evaluating a solvent or potential alternative is the
ACS GCIPR interactive solvent guide (depicted below). This tool allows permits interactive solvent selection based
upon the Principal Component Analysis (PCA) of the solvent’s physical
properties. Solvents which are close to each other in the map have similar
physical and chemical properties, whereas distant solvents are significantly
different. In addition, other data including the physical poperties,
functional groups, and environmental data has been included to aid nthe
rational selection of solvents. This tool is further defined in
"Toward a More Holistic Framework for Solvent Selection". Diorazio, L. J.; Hose, D. R. J.; Adlington, N. K., Org. Process Res. Dev.2016, 20, 760-773.
Solvent Literature:
"CHEM21's selection guide of classical- and less classical-solvents". Prat, D.; Wells, A.; Hayler, J.; Sneddon, H.; McElroy, C. R.; Abou-Shehada, S.; Dunn, P. J. Green Chem. 2016, 18, 288-296. (open access)
"GSK: Updating and Further Expanding GSK's Solvent Sustainability Guide". Alder, C. M.; Hayler, J. D.; Henderson, R. K.; Redman, A. M.; Shukla, L.; Shuster, L. E.; Sneddon, H. F.Green Chem. 2016, DOI: 10.1039/C6GC00611F.
"Pfizer: Green chemistry tools to influence a medicinal chemistry and research chemistry based organisation". Alfonsi, K.; Colberg, J.; Dunn, P. J.; Fevig, T.; Jennings, S.; Johnson, T. A.; Kleine, H. P.; Knight, C.; Nagy, M. A.; Perry, D. A.; Stefaniak, M. Green Chem . 2008, 10, 31-36.
"Sanofi's Solvent Selection Guide: A Step Toward More Sustainable Processes". Prat, D.; Pardigon, O.; Flemming, H.; Letestu, S.; Ducandas, V.; Isnard, P.; Guntrum, E.; Senac, T.; Ruisseau, S.; Cruciani, P.; Hosek, P. Org. Proc. Res. Dev . 2013, 17, 1517-1525.
"AstraZeneca: Toward a More Holistic Framework for Solvent Selection". Diorazio, L. J.; Hose, D. R. J.; Adlington, N. K. Org. Proc. Res. Dev. 2016, ASAP (open access)
"NMR Chemical Shifts of Trace Impurities: Industrially Preferred Solvents Used in Process and Green Chemistry (peaks of residual solvents in 6 different NMR solvents)". Babij, N. R.; McCusker, E. O.; Whiteker, G. T.; Canturk, B.; Choy, N.; Creemer, L. C.; De Amicis, C. V.; Hewlett, N. M.; Johnson, P. L.; Knobelsdorf, J. A.; Li, F.; Lorsbach, B. A.; Nugent, B. M.; Ryan, S. J.; Smith, M. R.; and Yang, Q. Org. Process Res. Dev., 2016, 20, 661-667. (open access)
"Development of GSK's NMR Guides – A tool to encourage the use of more sustainable solvents". Gottlieb, H. E.; Graczyk-Millbrandt, G.; Inglis, G. A.; Nudelman, A.; Perez, D.; Qian, Y.; Shuster, L. E.; Sneddon, H. F.; Upton, R. J.Green Chem. 2016 DOI: 10.1039/C6GC00446F.
"A convenient guide to help select replacement solvents for dichloromethane in chromatography". Taygerly, J. P.; Miller, L. M.; Yee, A.; Peterson, E. A. Green Chem. 2012, 14, 3020-3025.
"Replacement of dichloromethane within chromatographic purification: a guide to alternative solvents". MacMillan, D. S; Murray, J.; Sneddon, H. F. ; Jamieson, C.; Watson, A. J. B. Green Chem. 2012, 14, 3016-3019.
"Development of a tripartite solvent blend for sustainable chromatography". Chardon, F. M.; Blaquiere, N.; Castanedo, G. M.; Koenig, S. G. Green Chem. 2014, 16, 4102-4105.
Free Green Chemistry MOOC – created by IMI CHEM21 consortium. Due to be launched on 13 th June – but the test version is available to view here: http://test-chem21-elearning.pantheon.io/ . Pharmaceutical Green Chemistry is biased although the information is generalizable to other disciplines or industries
Reagent Selection:
Selecting the most sustainable reagent to use for organic chemistry
transformations requires the assessment of many factors including atom
efficiency, toxicology, safety, waste products, sustainable feedstocks, and
more. Industrial multidisciplinary chemists, as members of the ACS GCIPR, have
compiled reagent guides to inform and assist organic chemists in the selection
of reagents for >19 transformations or procedures.
Each guide, in the
collection of guides, is a comprehensive resource composed of:
A general overview of the transformation
A Venn diagram representation
General literature reviews
Special considerations (eg. safety) and green criteria
"Development of GSK's Reagent Guides – Embedding Sustainability into Reagent Selection". Adams, J. P.; Alder, C. M.; Bullion, A. M.; Campbell-Crawford, M.; Darcy, M. G.; Hayler, J. D.; Henderson, R. K.; Oare, C. A.; Pendrak, I.; Redman, A. M.; Shuster, L. E.; Sneddon, H. F.; Walker, M. D. Green Chem. 2013, 15, 1542-1549 .
"Development of GSK's Acid and Base Selection Guides". Henderson, R. K.; Hill, A. P.; Redman, A. M.; Sneddon, H. F. Green Chem. 2015, 17, 945-949.
"Evaluation of Alternative Solvents in Common Amide Coupling Reactions: Replacement of Dichloromethane and N, N -Dimethylformamide" MacMillan, D. S.; Murray, J.; Sneddon, H. F.; Jamieson, C.; Watson, A. J. B. Green Chem. 2013, 15, 596-600 (open access).
"Development of a Solvent Selection Guide for Aldehyde-based Direct Reductive Amination Processes". McGonagle, F. I.; MacMillan, D. S.; Murray, J.; Sneddon, H. F.; Jamieson, C.; Watson, A. J. B. Green Chem. 2013, 15, 1159-1165.
Biocatalysis guide:
Biocatalysis is a key green technology for modern sustainable organic
syntheses. The
Biocatalysis Guide
is a simple double-sided, single-sheet guide to the currently most used enzyme
classes amongst the ACS GCI member companies. It has been produced to be an
easy-to-follow guide for chemists who have not had significant exposure to
biocatalysis, showing generic transformations that are available so these can
be factored into retrosynthetic analysis.
Med Chem:
All parts of pharmaceutical development can be made more sustainable. A great
example of this is the ACS GCIPR Medicinal Chemistry Team’s approaches to
greening medicinal chemistry. The team produced
this quick guide
covering purification, solvent selection, reagents, energy and resources.
Process Mass Intensity:
Process mass intensity (PMI) is the key green mass-based metric for measuring
the resource usage impact of a synthetic chemistry process.
$$PMI = \frac{Mass of Raw Materials Input}{Mass of Product}$$ The PMI calculator
enables organic chemists to quickly determine the PMI number from the raw
material inputs and final product yield. The calculator accommodates
multi-step convergent syntheses and includes breakdown of solvent, reagents,
and water PMI. These calculations are an invaluable method to drive
development of more sustainable processes and to track the mass efficiency for
a synthetic procedure.Process mass intensity data has been gathered to provide
benchmarking data for the small-molecule, oligonucleotide, peptide, and
monoclonal antibody therapeutic classes.
The PMI prediction tool (depicted below) provides a simple and accessible means of predicting the mass
efficiency of proposed synthetic routes. The tool is built from a dataset of
nearly two thousand multi-kilo reactions provided by pharmaceutical, biotech,
and manufacturingompanies via the ACS GCIPR as well as extracted from the
literature. By defining a sequenceof reactions and their corresponding
reaction type, it is possible to estimate a plausible PMI for ay proposed or
unoptimized organic chemistry route. This ability to virtually screen
differentrspective routes for efficiency allows organic chemists to focus
their resources on a few poising synthetic approaches.
This process is elaborated in
"The PMI Predictor app to enable green-by-design chemical synthesis". Borovika, A.; Albrecht, J.; Li, J.; Wells, A. S.; Briddell, C.; Dillon, B.
R.; Diorazio, L. J.; Gage, J. R.; Gallou, F.; Koenig, S. G.; Kopach, M. E.;
Leahy, D. K.; Martinez, I.; Olbrich, M.; Piper, J. L.; Roschangar, F.; Sherer,
E. C.; Eastgate, M. D. Nature Sustainability. 2019 , 2,
1034–1040
Green Chemistry Innovation Scorecard Calculator:
Green Chemistry Innovation Scorecard Calculator
is a slightly different approach to accounting for PMI by focusing on waste. A
joint effort by the IQ Consortium, ACS GCI Pharmaceutical Roundtable, and
academic leaders, this Green Chemistry Innovation Scorecard web calculator
illustrates how green chemistry and engineering innovation can reduce waste
mass during bulk active pharmaceutical manufacture. The calculator uses a
statistical analysis of 64 bulk active pharmaceutical manufacturing processes
encompassing 703 steps across 12 companies to provide a relative process
greenness score. This score may then be used as a means of making meaningful
comparisons between different processes and their associated waste
reductions.
Green and Sustainable Medicinal Chemistry: Methods, Tools and Strategies for the 21st Century Pharmaceutical Industry edited by Louise Summerton, Helen F. Sneddon, Leonie C. Jones and James H. Clark; book published by Royal Society of Chemistry, 2016 DOI: 10.1039/9781782625940
Green Chemistry Strategies for Drug Discovery edited by Emily A. Peterson, Julie B. Manley, book published by Royal Society of Chemistry, 2015 DOI: 10.1039/9781782622659