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Production of chemicals via fermentation has been evolving over the past 30 years in search of economically viable systems. Thus far, there have been few industrially relevant chemicals that have seen commercialization, examples being lactic acid and ethanol. Currently, many of these fermentation processes still compete with food sources. In order to reduce this competition fermentation of alternative feedstocks, such as lignocellulosic biomass must to be utilized. Hemicellulosic sugars can be employed effectively for the production of chemicals by incorporating nonphosphorylative metabolism. This review covers nonphosphorylative metabolism, the pathways and enzymes involved, as well as the products that have been produced using nonphosphorylative metabolism.