Marshall D. Gates Jr. (1915–2003) was an American

chemist A chemist (from Greek ''chēm(ía)'' alchemy; replacing ''chymist'' from Medieval Latin ''alchemist'') is a graduated scientist trained in the study of chemistry, or an officially enrolled student in the field. Chemists study the composition of ...

, holding the position of C.F. Houghton Professor of Chemistry at the

University of Rochester The University of Rochester is a private university, private research university in Rochester, New York, United States. It was founded in 1850 and moved into its current campus, next to the Genesee River in 1930. With approximately 30,000 full ...

. He was an organic chemist whose research was in the field of natural product synthesis. He is best known for publishing the first total synthesis of morphine in 1952.

Biography

Marshall Gates was born in 1915 in

Boyne City, Michigan Boyne City () is a city in Charlevoix County, Michigan, Charlevoix County in the U.S. state of Michigan. The population was 3,816 at the 2020 United States census, 2020 census, making it the largest city in Charlevoix County. Boyne City is locat ...

. He received his undergraduate training at

Rice University William Marsh Rice University, commonly referred to as Rice University, is a Private university, private research university in Houston, Houston, Texas, United States. Established in 1912, the university spans 300 acres. Rice University comp ...

and his masters and doctoral degrees from

Harvard University Harvard University is a Private university, private Ivy League research university in Cambridge, Massachusetts, United States. Founded in 1636 and named for its first benefactor, the History of the Puritans in North America, Puritan clergyma ...

. He married Martha L. Meyer with whom he had two sons and two daughters. From 1941 to 1949 he taught at

Bryn Mawr College Bryn Mawr College ( ; Welsh language, Welsh: ) is a Private college, private Women's colleges in the United States, women's Liberal arts colleges in the United States, liberal arts college in Bryn Mawr, Pennsylvania, United States. Founded as a ...

at which point he moved to the

where he remained until his retirement in 1981. From 1943 to 1946 he did work for the National Defense Council and served as editor in chief of the

Journal of the American Chemical Society The ''Journal of the American Chemical Society'' (also known as JACS) is a weekly peer-reviewed scientific journal that was established in 1879 by the American Chemical Society. The journal has absorbed two other publications in its history, the ...

from 1949 to 1969. In honor of his death in 2003, a named professorship was established at the University of Rochester Department of Chemistry.

Morphine Total Synthesis

Gates's

total synthesis Total synthesis, a specialized area within organic chemistry, focuses on constructing complex organic compounds, especially those found in nature, using laboratory methods. It often involves synthesizing natural products from basic, commercially ...

morphine Morphine, formerly also called morphia, is an opiate that is found naturally in opium, a dark brown resin produced by drying the latex of opium poppies (''Papaver somniferum''). It is mainly used as an analgesic (pain medication). There are ...

was the first of its kind and an important confirmation of the structural determination made by Robert Robinson some 27 years prior. The synthesis was based on the construction of a cyanodiketone from the dihydroxynaphthalene shown below. The key step was a high-pressure Diels-Alder reaction with

butadiene 1,3-Butadiene () is the organic compound with the formula CH2=CH-CH=CH2. It is a colorless gas that is easily condensed to a liquid. It is important industrially as a precursor to synthetic rubber. The molecule can be viewed as the union of two ...

that established the fused ring system core. Reductive coupling between the

hydroxyl In chemistry, a hydroxy or hydroxyl group is a functional group with the chemical formula and composed of one oxygen atom covalently bonded to one hydrogen atom. In organic chemistry, alcohols and carboxylic acids contain one or more hydroxy ...

and

cyano In chemistry, cyanide () is an inorganic chemical compound that contains a functional group. This group, known as the cyano group, consists of a carbon atom triple-bonded to a nitrogen atom. Ionic cyanides contain the cyanide anion . This a ...

groups furnished the ethylamine bridge and further elaboration (including an arduous epimerization of the highlighted

stereocenter In stereochemistry, a stereocenter of a molecule is an atom (center), axis or plane that is the focus of stereoisomerism; that is, when having at least three different groups bound to the stereocenter, interchanging any two different groups cr ...

) established the so-called "Gates Intermediate." Syntheses published thereafter focused, for a time, on improvements to the synthesis of this intermediate as well as the final steps. Gates synthesis

References

# # Nicolaou, K.C. and Montagon T. ''Molecules that Changed the World''. Germany: Wiley-VCH, 2008. # Gates, M.D.; Tschudi, G. ''J. Am. Chem. Soc.'', 1956, ''78'' (7), pp 1380–1393. # "Morphine and Codeine," Baran Lab Presentation
Link

Biography

Morphine Total Synthesis

References

Further reading