Albert Eschenmoser

Albert Jakob Eschenmoser (born 5 August 1925) is a Swiss organic chemist best known for his work on the synthesis of complex heterocyclic natural compounds, most notably vitamin B12. In addition to his significant contributions to the field of organic synthesis, Eschenmoser pioneered work in the Origins of Life (OoL) field with work on the synthetic pathways of artificial nucleic acids. Before retiring in 2009, Eschenmoser held tenured teaching positions at the ETH Zurich and The Skaggs Institute for Chemical Biology at The Scripps Research Institute in La Jolla, California as well as visiting professorships at the University of Chicago, Cambridge University, and Harvard.

Albert Eschenmoser
Born (1925-08-05) 5 August 1925
Erstfeld, Switzerland
NationalitySwiss
Alma materETH Zurich
Known forEschenmoser's salt
Eschenmoser fragmentation
Eschenmoser sulfide contraction
Eschenmoser–Claisen rearrangement
Synthesis of vitamin B12 (along with Woodward)
AwardsMarcel Benoist Prize (1972)
Davy Medal (1978)
Wolf Prize in Chemistry (1986)
Scientific career
FieldsOrganic chemistry
InstitutionsETH Zurich
ThesisZur säurekatalysierten Zyklisierung bei Mono- und Sesquiterpenverbindungen (1952)
Doctoral advisorLavoslav Ružička
Doctoral studentsScott E. Denmark
Ernst-Ludwig Winnacker
Andreas Pfaltz

Early work and Vitamin B12 Synthesis

Eschenmoser began his scientific career as a graduate student in the laboratory of Leopold Ružička, at the Eidgenossische Technische Hochschule (ETH) in Zurich. Ruzicka was a notable organic chemist himself having been awarded the Nobel Prize in Chemistry in 1939 for his work on the synthesis of androsterone and testosterone. Eschenmoser’s early work on the cyclization of unsaturated, conjugated hydrocarbons directly contributed to advances in the field of terpene chemistry and provided insight into steroid biosynthesis.[1][2]

In the early 1960s, having become Professor of General Organic Chemistry at ETH, Eschenmoser began work on what was the most complex natural product synthesized at the time—vitamin B12. In a remarkable collaboration with his colleague Robert Burns Woodward at Harvard University, a team of almost one hundred students and postdoctoral workers worked for many years on the synthesis of this molecule. At the time, a significant obstacle to the synthesis of vitamin B12 had been the difficulty in forming the macrocyclic ring closure necessary to complete the corrin ring structure at the center of the molecule. However during this time, Eschenmoser and his collaborators discovered a number reaction conditions under which this bond could be formed with a high degree of stereospecificity, including a novel photochemical process known as the “A/D variant.”[3] The work was finally published in 1973, and it marked a landmark in the history of organic chemistry.

The Eschenmoser fragmentation, the Eschenmoser sulfide contraction and Eschenmoser's salt are named after him.

Origins of Life (OoL) Research

A particularly vexing question in the study of the chemical origins of life is the selection of ribose, which forms the backbone of the nucleic acids found in modern biological systems. Eschenmoser’s work on a variant of the formose reaction that produces phosphorylated ribose in relatively significant concentrations has provided significant insight. Eschenmoser and colleagues demonstrated that phosphorylated glycoaldehyde when condensed with glyceraldehyde (a product of successive formaldehyde condensations) produces phosphorylated ribose differentially, providing a plausible explanation for the origin of both the sugar ribose, and the phosphate group required to polymerize monomeric nucleotides, in modern biochemistry.[4]

TNA and Artificial Nucleic Acids

Eschenmoser developed synthetic pathways for artificial nucleic acids, specifically modifying the sugar backbone of the polymer.[5] Having developed a number of structural alternatives to the naturally occurring nucleic acids, Eschenmoser and his colleagues were able to contrast the properties of these synthetic nucleic acids with naturally occurring ones to effectively determine the properties of RNA and DNA vital to modern biochemical processes. This work demonstrated that hydrogen-bonding interactions between the base-paring surfaces of the nucleobases alone might not have provided sufficient selection pressure to lead to the eventual rise of ribose in the structure of modern nucleic acids. He determined that pentose sugars, particularly ribose, conform to a geometry that contributes significantly to the helical structure of DNA by optimizing base-pair stacking distances in naturally occurring oligonucleotides. These base-stacking interactions orient and stabilize the base-paring surfaces of the nucleobases (A, G, C, T or U in RNA) and give rise to the canonical Watson-Crick base-paring rules that are well understood today.

Threose nucleic acid is an artificial genetic polymer invented by Eschenmoser. TNA strings composed of repeating threose sugars linked together by phosphodiester bonds. Like DNA and RNA, the molecule TNA can store genetic information in strings of nucleotide sequences. John Chaput, a professor at UC Irvine, has theorized that issues concerning the prebiotic synthesis of ribose sugars and the non-enzymatic replication of RNA may provide circumstantial evidence of an earlier genetic system more readily produced under primitive earth conditions. TNA could have been an early pre-DNA genetic system.[6]

Awards
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gollark: BIGLY.
gollark: ```pythonprint(9**9**9**9)```
gollark: 15 might be interesting, I think my simple approach might dominate there.
gollark: 100 chars is perhaps too high, you can do a *lot*.

References
  1. Eschenmoser, Albert (1955). "Eine Stereochemische Interpretation der biogenetischen Isoprenregel bei den Triterpenen" (PDF). Helvetica Chimica Acta. 38: 1890. doi:10.1002/hlca.19550380728.
  2. Eschenmoser, Albert (2007). "The Search for the Chemistry of Life's Origin". Tetrahedron. 63 (52): 12821–12844. doi:10.1016/j.tet.2007.10.012.
  3. Eschenmoser, Albert (1971). "Studies on Organic Synthesis, International Congress of Pure and Applied Chemistry : Special lectures presented at Boston, USA". 2: 26–30. Cite journal requires |journal= (help)
  4. Muller (1990). "Synthesis of IH-Cyclopropal[g]quinoline via Trapping of an ortho-Quinodimethane". Helvetica Chimica Acta. 73: 1410–1468. doi:10.1002/hlca.19900730526.
  5. Eschenmoser, Albert (1988). "Vitamin B12: Experiments Concerning the Origin of Its Molecular Structure". Angew. Chem. Int. Ed. 27: 5–39. doi:10.1002/anie.198800051.
  6. Harth, Richard (January 8, 2012). "Simpler times: Did an earlier genetic molecule predate DNA and RNA?". Retrieved 11 November 2016.
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