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 scientist trained in the study of chemistry. Chemists study the composition of matter and its properties. Chemists carefully describe t ...

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

University of Rochester The University of Rochester (U of R, UR, or U of Rochester) is a private university, private research university in Rochester, New York. The university grants Undergraduate education, undergraduate and graduate degrees, including Doctorate, do ...

. 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 in the U.S. state of Michigan. The population was 3,816 at the 2020 census. The city is located at the southeastern end of Lake Charlevoix where Boyne River drains into the lake. History The are ...

. He received his undergraduate training at

Rice University William Marsh Rice University (Rice University) is a private research university in Houston, Texas. It is on a 300-acre campus near the Houston Museum District and adjacent to the Texas Medical Center. Rice is ranked among the top universities ...

and his masters and doctoral degrees from

Harvard University Harvard University is a private Ivy League research university in Cambridge, Massachusetts. Founded in 1636 as Harvard College and named for its first benefactor, the Puritan clergyman John Harvard, it is the oldest institution of high ...

. 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: ) is a women's liberal arts college in Bryn Mawr, Pennsylvania. Founded as a Quaker institution in 1885, Bryn Mawr is one of the Seven Sister colleges, a group of elite, historically women's colleges in the United ...

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'' 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 ''Journal of Analytic ...

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 is the complete chemical synthesis of a complex molecule, often a natural product, from simple, commercially-available precursors. It usually refers to a process not involving the aid of biological processes, which distinguishes i ...

morphine Morphine is a strong opiate that is found naturally in opium, a dark brown resin in poppies (''Papaver somniferum''). It is mainly used as a pain medication, and is also commonly used recreationally, or to make other illicit opioids. T ...

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)2. 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 vi ...

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 hydro ...

and

cyano Cyanide is a naturally occurring, rapidly acting, toxic chemical that can exist in many different forms. In chemistry, a cyanide () is a chemical compound that contains a functional group. This group, known as the cyano group, consists of 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 c ...

) 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