Tribute to Dr. James Cullen Martin

July 15, 2024·Devraj Bagchi
Devraj Bagchi
Education

Who is James Cullen Martin?

Courtesy of Akiba (2006)

Photo taken at the author’s office in Hiroshima and that of J.C. Martin Symposium at Vanderbilt reported in C & EN News.

Courtesy of Akiba (2006)

James Cullen Martin (1928-1999) was a prominent figure in the field of organic chemistry, known for his pioneering work on hypervalent compounds. Born in Dover, Tennessee, Martin's academic journey began at Vanderbilt University, where he earned both his bachelor's and master's degrees. He continued his education at Harvard University, earning a Ph.D. under the mentorship of Paul Bartlett. His career at the University of Illinois at Urbana-Champaign (UIUC) spanned from instructor to professor, eventually leading the Division of Organic Chemistry.1

Contributions

Martin’s contributions to the field are significant, particularly his invention of the Dess-Martin Periodinane (DMP), a key reagent in organic synthesis.

Dess-Martin Periodinane (DMP) has three acetoxy groups bonded to the central iodine atom. DMP is highly soluble in DCM which makes DCM, the ideal solvent to use.

DMP and DCM

Dess-Martin Periodinane (DMP) has three acetoxy groups bonded to the central iodine atom. DMP is highly soluble in DCM which makes DCM, the ideal solvent to use.

Martin's research focused on the chemistry of hypervalent compounds, exploring new compounds and bonding main group elements. In 1983, along with his doctoral student Daniel Benjamin Dess, he developed DMP, an efficient and selective reagent for the oxidation of alcohols. This invention addressed several limitations of existing methods, offering a straightforward synthesis and mild reaction conditions. The preparation of DMP involved treating 2-iodobenzoic acid with potassium bromate in sulfuric acid, followed by reaction with acetic anhydride and acetic acid, yielding a high-purity product with an 87% overall yield.2

Note: Dess-Martin Periodinane is written in with in it’s shortform.

Creation of DMP in a 2 step synthesis.

Note: Dess-Martin Periodinane is written in with in it’s shortform.

DMP's efficacy lies in its ability to oxidize primary alcohols to aldehydes and secondary alcohols to ketones under mild conditions. The oxidation reactions are performed in dichloromethane (DCM) at room temperature, simplifying the process and avoiding the long reaction times and complex workup procedures associated with other methods. DMP is highly selective, particularly for benzylic alcohols, and its use avoids the generation of toxic by-products, making it environmentally friendly. 2

An environmentally friendly and mild selective oxidation method.

Selective Oxidation of Alcohols to Aldehydes and Ketones

An environmentally friendly and mild selective oxidation method.

Beyond DMP, Martin made significant contributions to the chemistry of hypervalent molecules. He is credited with developing Martin's sulfurane, another valuable reagent in organic synthesis.3

His work earned him several prestigious awards, including a Guggenheim fellowship and the Alexander von Humboldt Foundation Research Prize. Martin's influence extended beyond his research; he served as chair of the Organic Division of the American Chemical Society and was a beloved mentor to many students and colleagues. 2

Personal Life

Martin's personal life was as rich as his professional one. He was born on January 14, 1928, in Dover, Tennessee, and served in the US Army from 1946 to 1950. During his service, he spent time in Kyoto, Japan, as a cultural liaison after World War II.3

Known for his gentle and generous character, Martin balanced his demanding career with a strong commitment to his family. He married June E. Martin, an occupational therapist, and together they had five children.3

His son, Professor Joseph V. Martin, now at Rutgers University, recalls his father's dedication both at home and in his professional life. Martin passed away on April 20, 1999, in Tampa, Florida, but his legacy continues through his family and the countless chemists he inspired.3

Courtesy of Akiba (2006)

Photo taken at Illnois

Courtesy of Akiba (2006)

Courtesy of Akiba (2006)

Photos taken at Hiroshima (two), Vanderbilt (home), and Kyoto.

Courtesy of Akiba (2006)

Martin's publication record is extensive, with 155 reports, including 99 in the Journal of the American Chemical Society (JACS), 22 in the Journal of Organic Chemistry, and 4 in Tetrahedron Letters. His work covered various themes, from anchimerically accelerated bond homolysis to the chemistry of sulfuranes and hypervalent iodine, phosphorus, and silicon compounds. Notable papers include his first publication with D.E. Pearson and J.F. Baxter in the Journal of Organic Chemistry (1952) and subsequent influential works in JACS and other leading journals.3

James Cullen Martin’s achievements and contributions to chemistry have left an indelible mark on the scientific community. His development of the Dess-Martin Periodinane revolutionized alcohol oxidation methods and continues to be a staple in laboratories worldwide. Martin’s dedication to research and education, combined with his compassionate nature, ensured that his legacy would be remembered for generations to come. As we celebrate his life and work, we honor a scientist whose innovations and mentorship profoundly impacted the field of organic chemistry.

Courtesy of Akiba (2006)

Waka prepared and written in memory of Professor James C. Martin.

Courtesy of Akiba (2006)

This Waka was prepared and written by the author for the ISOCS-21 Conference in Madrid in July 2004, in memory of Professor James C. Martin. A Waka is a traditional Japanese short poem consisting of 31 phonetic characters. This is based on a well-known Waka in the Man’yōshū, the oldest collection of Waka, which is supported by the Emperor. The Japanese reading is shown in the Romanized form, followed by a translation.

JP Translation:
幸いのいかなる人か諸国の化学者集い千家悲しむ
Sakiwai no ikanaru hito ka morokuni no kemisuto tudoi sennge kanashimu

EN Translation:
What a happy and beloved person he was! Hundreds of chemists from many countries gather to mourn him and admire his accomplishments in chemistry.

Rest in Peace,
Dr. J.C. Martin

References

1. University of Illinois Archives, "Martin, James C." Available at: https://archives.library.illinois.edu/archon/?p=creators/creator&id=3886. Accessed June 29, 2024.

2. Dess, D. B.; Martin, J. C. Readily Accessible 12-I-51 Oxidant for the Conversion of Primary and Secondary Alcohols to Aldehydes and Ketones. J. Org. Chem. 1983, 48, 4155–4156. DOI: 10.1021/jo00356a052.

3. Akiba, K.-y. Memoirs of Professor James Cullen Martin. Phosphorus, Sulfur, and Silicon 2006, 181, 1201–1215. DOI: 10.1080/10426500500326321.

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