David Milstein

David Milstein (born June 4, 1947) is an Israeli chemist best known for his research on metal-mediated activation and functionalization of very strong chemical bonds. He is recipient of the 2012 Israel Prize and the 2016 ENI Award for Protection of the Environment.

Biography

Milstein, who immigrated with his family to the newly founded state of Israel at the age of two, was born (1947) in the city of Ulm, in post-war Germany, where his family took refuge after being displaced during the Holocaust. Milstein was first fascinated by chemistry when attending high school in the town of Rehovot where “an enthusiastic, old-fashioned chemistry teacher who didn’t care much about orbitals” inspired him “with vivid, thought-provoking experiments”.^[1] Pursuing his interest, Milstein received B.Sc., M.Sc., and Ph.D. degrees in chemistry from the Hebrew University of Jerusalem. He carried out postdoctoral research in the U.S. at the University of Iowa and at Colorado State University. In 1979, Milstein joined DuPont Central Research & Development in Wilmington, Delaware, where he became a group leader in the homogeneous catalysis area. In 1987, he took up an academic position at the Weizmann Institute of Science in Israel, where he is now director of the Kimmel Center for Molecular Design and the Israel Matz Professorial Chair of Organic Chemistry.

Research

Milstein has authored Over 320 publications in peer-reviewed journals . He and his coworkers have developed many group 8, 9, and 10 transition-metal complexes with specifically designed ligands that have proven useful to activate strong C-C, C-H, C-F, N-H, and O-H bonds.

The C-C Bond

While a postdoc, Milstein and his adviser, John Kenneth Stille, discovered the Stille reaction for new carbon-carbon bond formation using a palladium catalyst to couple an organic halide with an organotin compound.^[2] This reaction is considered a very useful method for new C-C bond formation and is now widely used in the synthesis of pharmaceuticals. His subsequent research on the C-C bond includes a 1993 publication describing insertion of a rhodium complex into a strong C-C bond using a pincer-type substrate that helps draw the metal center to the hard-to-access C-C bond.^[3] This paper is considered a classic for establishing a general strategy for C-C activation in homogeneous systems.^[4] Milstein's research focused also on bonds between carbon and other elements. An example is his work on activation of the notoriously inert C-F bond in reactions of fluorinated benzenes with silanes or hydrogen using a rhodium catalyst.^[5]

New Route to Amide Synthesis

Milstein had dealt in his research with N-H and O-H activation, inserting iridium complexes into the N-H bond of ammonia and the O-H bond of water and converting primary alcohols to esters with liberation of hydrogen using a pincer-type ruthenium catalyst.^[6] Using the same pincer-like ruthenium catalyst, Milstein and co-workers devised a new method for making amides, based on coupling alcohols and amines.^[7] This research was selected by Science magazine as one of the top ten breakthroughs of 2007,^[8] being praised both for its cleanliness and selectivity, eschewing the harsh reagents and conditions usually required to make amides and creating H2 gas as the only by-product.

Light-induced Water Splitting

Discovery of an efficient artificial catalyst for the sunlight-driven splitting of water is a major goal of renewable energy research, as it would allow generation of energy-dense hydrogen without investment of electricity. Recently, Milstein and his co-workers have described a solution-phase reaction scheme that leads to the stoichiometric liberation of hydrogen and oxygen in consecutive thermal- and light-driven steps mediated by mononuclear, well-defined ruthenium complexes, in essence establishing a new light-driven water splitting strategy that does not require a sacrificial chemical in the process.^[9][10]

Honors and awards

Upon receipt of the ENI Award for Protection of the Environment, Rome 2016

• 2016 recipient of the ENI Award for Protection of the Environment^[11]
• 2012 Israel Prize recipient in Chemistry and Physics
• The Humboldt Research Award by the Alexander Von Humboldt Foundation, 2011
• Fellow of the Royal Society of Chemistry, 2010
• The 2010 Royal Society of Chemistry Sir Geoffrey Wilkinson Award
• The 2007 American Chemical Society Award in Organometallic Chemistry
• Research selected by Science among the top 10 major scientific breakthroughs of the year 2007
• The 2006 Israel Chemical Society Prize
• Election to the German Academy of Sciences Leopoldina, 2006
• Miller Visiting Professor, Miller Institute, UC Berkeley, spring 2006
• The I.M. Kolthoff Prize in Chemistry, 2002 (awarded by Technion, Israel Institute of Technology)
• The Paolo Chini Memorial Award 1999 (awarded by the Italian Chemical Society)

Major publications

• D. Milstein, J. K. Stille" A general, selective, and facile method for ketone synthesis from acid chlorides and organotin compounds catalyzed by palladium, J. Am. Chem. Soc 100 (11), 3636 – 3638 (1978).
• Gozin, M.; Weisman, A.; Ben-David, Y.; Milstein, D. (1993). "Activation of a carbon–carbon bond in solution by transition-metal insertion". Nature. 364: 699–701. doi:10.1038/364699a0. 
• Gozin, M.; Aizenberg, M.; Liou, S.-Y.; Weisman, A.; Ben-David, Y.; Milstein, D. (1994). "Transfer of methylene groups promoted by metal complexation". Nature. 370: 42–44. doi:10.1038/370042a0. 
• Aizenberg, M.; Milstein, D. (1994). "Catalytic activation of carbon-fluorine bonds by a soluble transition metal complex". Science. 265: 359–361. PMID 17838035. doi:10.1126/science.265.5170.359. 
• Tollner, K.; Popovitz-Biro, R.; Lahav, M.; Milstein, D. (1997). "Impact of molecular order in Langmuir-Blodgett films on catalysis". Science. 278: 2100–2102. doi:10.1126/science.278.5346.2100. 
• Zhang, J.; Leitus, G.; Ben-David, Y.; Milstein, D. (2005). "Facile conversion of alcohols into esters and dihydrogen catalyzed by new ruthenium complexes". J. Am. Chem. Soc. 127: 10840–10841. doi:10.1021/ja052862b. 
• Gunanathan, C.; Ben-David, Y.; Milstein, D. (2007). "Direct synthesis of amides from alcohols and amines with liberation of H2". Science. 317: 790–792. PMID 17690291. doi:10.1126/science.1145295. 
• Poverenov, E.; Efremenko, I.; Frenkel, A. I.; Ben-David, Y.; Shimon, L. J. W.; Leitus, G.; Konstantinovski, L.; Martin, J. M. L.; Milstein, D. (2008). "Evidence for a terminal Pt(IV)-oxo complex exhibiting diverse reactivity". Nature. 455: 1093–1096. doi:10.1038/nature07356. 
• Kohl, S. W.; Weiner, L.; Schwartsburd, L.; Konstantinovski, L.; Shimon, L. J. W.; Ben-David, Y.; Iron, M. A.; Milstein, D. (2009). "Consecutive thermal H2 and light-induced O2 evolution from water promoted by a metal complex". Science. 324: 74–77. PMID 19342584. doi:10.1126/science.1168600. 

Personal

Son of Musia and Abraham and younger brother of Lea, Milstein married to Adi Milstein in 1971, with whom he has three children: Nofit (b. 1972), Oren (b. 1976, cofounder of StemRad), and Abraham (b. 1983). He resides in the town of Rehovot in Israel.

References