Richard F. Heck
Encyclopedia
Richard Fred Heck is an American chemist noted for the discovery and development of the Heck reaction
, which uses palladium
to catalyze organic chemical reaction
s that couple aryl halides with alkene
s.
Heck was jointly awarded the Nobel Prize in Chemistry
on October 6, 2010, with the Japanese chemists Ei-ichi Negishi
and Akira Suzuki
, for their work in palladium-catalyzed coupling reactions
in organic synthesis
.
in 1931. He earned both his bachelor's degree
(1952) and his doctor of philosophy
degree (1954) at the University of California, Los Angeles
(UCLA), working under the supervision of Dr. Saul Winstein
. After two periods of postdoctoral research at the ETH
in Zurich, Switzerland, and then back at UCLA, Heck took a position with the Hercules Corporation in Wilmington, Delaware
in 1957. After productive research work at Hercules, he was hired by the University of Delaware
's Department of Chemistry and Biochemistry in 1971. Heck was a professor
of chemistry
at the University of Delaware until his retirement in the year 1989.
The development of the Heck reaction
began with Heck's investigations of the coupling of arylmercury compounds with olefins using palladium
as a catalyst during the late 1960s.
This work was published in a series of seven consecutive articles in the Journal of the American Chemical Society
(JACS) for which Heck was the sole author.
During the early 1970s Mizoroki independently reported the use of the less toxic aryl halides as the coupling partner in the reaction. and Heck During his career, Heck continued to improve the transformation, developing it into a powerful synthetic method for organic synthesis.
The importance of this reaction grew slowly in the organic synthesis community. In 1982, Heck was able to write an Organic Reactions
chapter that covered all the known instances in just 45 pages. By 2002, applications had grown to the extent that the Organic Reactions chapter published that year, limited to intramolecular Heck reactions, covered 377 pages.
Today, the Heck reaction
stands as one of the widely used methods for the creation of carbon-carbon bond
s in the synthesis of organic chemicals
. This reaction has been subject to numerous scientific review articles, including a ~600 page monograph dedicated to this subject published in 2009.
-catalyzed coupling reactions, including those of aryl halides with derivatives of boronic acid
(Suzuki–Miyaura coupling
), organotin
reagents (Stille coupling
), organomagnesium compounds (Kumada-Corriu coupling
), silane
s (Hiyama coupling
), and organozincs (Negishi coupling
), as well as with amines (Buchwald–Hartwig amination) and alcohols. These palladium-catalyzed coupling reactions are now widely practiced in organic synthesis, including in the chemical engineering
production of certain organic compound
s in factories.
Of the several reactions developed by Heck, the greatest societal impact has been from the palladium-catalyzed coupling of an alkyne with an aryl halide
. This is the reaction that was used to couple fluorescent dyes to DNA bases, allowing the automation of DNA sequencing
and the examination of the human genome
. In Sonogashira's original report of what is now known as the Sonogashira coupling
, his group modified an alkyne coupling procedure previously reported by Heck, by adding a copper(I) salt.
Heck's contributions are not limited to the activation of halides by the oxidative addition of palladium. Heck was the first to fully characterize a π-allyl metal complex, and the first to elucidate the mechanism of alkene hydroformylation
. Hydroformylation is currently used to produce about 15 billion pound
s of alcohols and aldehydes each year.
with Ei-ichi Negishi
and Akira Suzuki
"for palladium-catalyzed cross couplings in organic synthesis." In 2011, Heck was awarded the Glenn T. Seaborg Medal
for his work on palladium-catalyzed cross couplings.
Richard Heck now resides and intends to retire in the Philippines
.
Heck reaction
The Heck reaction is the chemical reaction of an unsaturated halide with an alkene and a base and palladium catalyst to form a substituted alkene. Together with the other palladium-catalyzed cross-coupling reactions, this reaction is of great importance, as it allows one to do substitution...
, which uses palladium
Palladium
Palladium is a chemical element with the chemical symbol Pd and an atomic number of 46. It is a rare and lustrous silvery-white metal discovered in 1803 by William Hyde Wollaston. He named it after the asteroid Pallas, which was itself named after the epithet of the Greek goddess Athena, acquired...
to catalyze organic chemical reaction
Chemical reaction
A chemical reaction is a process that leads to the transformation of one set of chemical substances to another. Chemical reactions can be either spontaneous, requiring no input of energy, or non-spontaneous, typically following the input of some type of energy, such as heat, light or electricity...
s that couple aryl halides with alkene
Alkene
In organic chemistry, an alkene, olefin, or olefine is an unsaturated chemical compound containing at least one carbon-to-carbon double bond...
s.
Heck was jointly awarded the Nobel Prize in Chemistry
Nobel Prize in Chemistry
The Nobel Prize in Chemistry is awarded annually by the Royal Swedish Academy of Sciences to scientists in the various fields of chemistry. It is one of the five Nobel Prizes established by the will of Alfred Nobel in 1895, awarded for outstanding contributions in chemistry, physics, literature,...
on October 6, 2010, with the Japanese chemists Ei-ichi Negishi
Ei-ichi Negishi
is a Japanese chemist who has spent most of his career at Purdue University, United States. He is best known for his discovery of the Negishi coupling. He was awarded the 2010 Nobel Prize in Chemistry "for palladium catalyzed cross couplings in organic synthesis" jointly with Richard F. Heck and...
and Akira Suzuki
Akira Suzuki (chemist)
is a Japanese chemist and Nobel Prize Laureate , who first published the Suzuki reaction, the organic reaction of an aryl- or vinyl-boronic acid with an aryl- or vinyl-halide catalyzed by a palladium complex, in 1979.-Life:...
, for their work in palladium-catalyzed coupling reactions
Palladium-catalyzed coupling reactions
Palladium compounds are used as a catalyst in many coupling reactions, usually as a homogeneous catalyst. Examples include:* Heck reaction between alkenes and aryl halides* Suzuki reaction between aryl halides and boronic acids...
in organic synthesis
Organic synthesis
Organic synthesis is a special branch of chemical synthesis and is concerned with the construction of organic compounds via organic reactions. Organic molecules can often contain a higher level of complexity compared to purely inorganic compounds, so the synthesis of organic compounds has...
.
Life and career
Heck was born in Springfield, MassachusettsSpringfield, Massachusetts
Springfield is the most populous city in Western New England, and the seat of Hampden County, Massachusetts, United States. Springfield sits on the eastern bank of the Connecticut River near its confluence with three rivers; the western Westfield River, the eastern Chicopee River, and the eastern...
in 1931. He earned both his bachelor's degree
Bachelor's degree
A bachelor's degree is usually an academic degree awarded for an undergraduate course or major that generally lasts for three or four years, but can range anywhere from two to six years depending on the region of the world...
(1952) and his doctor of philosophy
Doctor of Philosophy
Doctor of Philosophy, abbreviated as Ph.D., PhD, D.Phil., or DPhil , in English-speaking countries, is a postgraduate academic degree awarded by universities...
degree (1954) at the University of California, Los Angeles
University of California, Los Angeles
The University of California, Los Angeles is a public research university located in the Westwood neighborhood of Los Angeles, California, USA. It was founded in 1919 as the "Southern Branch" of the University of California and is the second oldest of the ten campuses...
(UCLA), working under the supervision of Dr. Saul Winstein
Saul Winstein
Saul Winstein was the Canadian chemist who discovered the Winstein reaction, in which he argued a non-classical cation was needed to explain the stability of the norbornyl cation. This fueled a debate with Herbert C. Brown over the existence of delocalized cations such as this. Richard F...
. After two periods of postdoctoral research at the ETH
ETH Zurich
The Swiss Federal Institute of Technology Zurich or ETH Zürich is an engineering, science, technology, mathematics and management university in the City of Zurich, Switzerland....
in Zurich, Switzerland, and then back at UCLA, Heck took a position with the Hercules Corporation in Wilmington, Delaware
Wilmington, Delaware
Wilmington is the largest city in the state of Delaware, United States, and is located at the confluence of the Christina River and Brandywine Creek, near where the Christina flows into the Delaware River. It is the county seat of New Castle County and one of the major cities in the Delaware Valley...
in 1957. After productive research work at Hercules, he was hired by the University of Delaware
University of Delaware
The university is organized into seven colleges:* College of Agriculture and Natural Resources* College of Arts and Sciences* Alfred Lerner College of Business and Economics* College of Earth, Ocean and Environment* College of Education and Human Development...
's Department of Chemistry and Biochemistry in 1971. Heck was a professor
Professor
A professor is a scholarly teacher; the precise meaning of the term varies by country. Literally, professor derives from Latin as a "person who professes" being usually an expert in arts or sciences; a teacher of high rank...
of chemistry
Chemistry
Chemistry is the science of matter, especially its chemical reactions, but also its composition, structure and properties. Chemistry is concerned with atoms and their interactions with other atoms, and particularly with the properties of chemical bonds....
at the University of Delaware until his retirement in the year 1989.
The development of the Heck reaction
Heck reaction
The Heck reaction is the chemical reaction of an unsaturated halide with an alkene and a base and palladium catalyst to form a substituted alkene. Together with the other palladium-catalyzed cross-coupling reactions, this reaction is of great importance, as it allows one to do substitution...
began with Heck's investigations of the coupling of arylmercury compounds with olefins using palladium
Palladium
Palladium is a chemical element with the chemical symbol Pd and an atomic number of 46. It is a rare and lustrous silvery-white metal discovered in 1803 by William Hyde Wollaston. He named it after the asteroid Pallas, which was itself named after the epithet of the Greek goddess Athena, acquired...
as a catalyst during the late 1960s.
This work was published in a series of seven consecutive articles in the Journal of the American Chemical Society
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 Analytical and Applied Chemistry and the American Chemical Journal...
(JACS) for which Heck was the sole author.
During the early 1970s Mizoroki independently reported the use of the less toxic aryl halides as the coupling partner in the reaction. and Heck During his career, Heck continued to improve the transformation, developing it into a powerful synthetic method for organic synthesis.
The importance of this reaction grew slowly in the organic synthesis community. In 1982, Heck was able to write an Organic Reactions
Organic Reactions
Organic Reactions is a secondary reference which synthesizes the organic chemistry literature around particular chemical transformations. Each chapter of Organic Reactions is devoted to a particular organic chemical reaction, and chapters provide exhaustive coverage of literature work in the form...
chapter that covered all the known instances in just 45 pages. By 2002, applications had grown to the extent that the Organic Reactions chapter published that year, limited to intramolecular Heck reactions, covered 377 pages.
Today, the Heck reaction
Heck reaction
The Heck reaction is the chemical reaction of an unsaturated halide with an alkene and a base and palladium catalyst to form a substituted alkene. Together with the other palladium-catalyzed cross-coupling reactions, this reaction is of great importance, as it allows one to do substitution...
stands as one of the widely used methods for the creation of carbon-carbon bond
Carbon-carbon bond
A carbon–carbon bond is a covalent bond between two carbon atoms. The most common form is the single bond: a bond composed of two electrons, one from each of the two atoms. The carbon–carbon single bond is a sigma bond and is said to be formed between one hybridized orbital from each...
s in the synthesis of organic chemicals
Organic compound
An organic compound is any member of a large class of gaseous, liquid, or solid chemical compounds whose molecules contain carbon. For historical reasons discussed below, a few types of carbon-containing compounds such as carbides, carbonates, simple oxides of carbon, and cyanides, as well as the...
. This reaction has been subject to numerous scientific review articles, including a ~600 page monograph dedicated to this subject published in 2009.
Palladium-catalyzed coupling reactions
Heck's work set the stage for a variety of other palladiumPalladium
Palladium is a chemical element with the chemical symbol Pd and an atomic number of 46. It is a rare and lustrous silvery-white metal discovered in 1803 by William Hyde Wollaston. He named it after the asteroid Pallas, which was itself named after the epithet of the Greek goddess Athena, acquired...
-catalyzed coupling reactions, including those of aryl halides with derivatives of boronic acid
Boronic acid
A boronic acid is an alkyl or aryl substituted boric acid containing a carbon–boron bond belonging to the larger class of organoboranes. Boronic acids act as Lewis acids. Their unique feature is that they are capable of forming reversible covalent complexes with sugars, amino acids, hydroxamic...
(Suzuki–Miyaura coupling
Suzuki reaction
The Suzuki reaction is the organic reaction of an aryl- or vinyl-boronic acid with an aryl- or vinyl-halide catalyzed by a palladium complex. It is widely used to synthesize poly-olefins, styrenes, and substituted biphenyls, and has been extended to incorporate alkyl bromides...
), organotin
Organotin
Organotin compounds or stannanes are chemical compounds based on tin with hydrocarbon substituents. Organotin chemistry is part of the wider field of organometallic chemistry. The first organotin compound was diethyltin diiodide, discovered by Edward Frankland in 1849...
reagents (Stille coupling
Stille reaction
The Stille reaction is a chemical reaction coupling an organotin compound with an sp2-hybridized organic halide catalyzed by palladium. The reaction is widely used in organic synthesis....
), organomagnesium compounds (Kumada-Corriu coupling
Kumada coupling
A Kumada coupling or Kumada-Corriu coupling is a cross coupling reaction in organic chemistry between an alkyl or aryl Grignard reagent and an aryl or vinyl halocarbon catalysed by nickel or palladium. This reaction is relevant to organic synthesis because it gives access to styrene derivatives...
), silane
Silane
Silane is a toxic, extremely flammable chemical compound with chemical formula SiH4. In 1857, the German chemists and Friedrich Woehler discovered silane among the products formed by the action of hydrochloric acid on aluminum silicide, which they had previously prepared...
s (Hiyama coupling
Hiyama coupling
In organic chemistry, a Hiyama coupling is a palladium or nickel-catalyzed cross coupling reaction of organosilanes with organic halides or triflates. Hiyama couplings were first reported by Yasuo Hatanaka and Tamejiro Hiyama in 1988....
), and organozincs (Negishi coupling
Negishi coupling
The Negishi coupling is a cross coupling reaction in organic chemistry involving an organozinc compound, an organic halide and a nickel or palladium catalyst creating a new carbon-carbon covalent bond:* The halide X can be chloride, bromine or iodine but also a triflate or acetyloxy group with as...
), as well as with amines (Buchwald–Hartwig amination) and alcohols. These palladium-catalyzed coupling reactions are now widely practiced in organic synthesis, including in the chemical engineering
Chemical engineering
Chemical engineering is the branch of engineering that deals with physical science , and life sciences with mathematics and economics, to the process of converting raw materials or chemicals into more useful or valuable forms...
production of certain organic compound
Organic compound
An organic compound is any member of a large class of gaseous, liquid, or solid chemical compounds whose molecules contain carbon. For historical reasons discussed below, a few types of carbon-containing compounds such as carbides, carbonates, simple oxides of carbon, and cyanides, as well as the...
s in factories.
Of the several reactions developed by Heck, the greatest societal impact has been from the palladium-catalyzed coupling of an alkyne with an aryl halide
Halide
A halide is a binary compound, of which one part is a halogen atom and the other part is an element or radical that is less electronegative than the halogen, to make a fluoride, chloride, bromide, iodide, or astatide compound. Many salts are halides...
. This is the reaction that was used to couple fluorescent dyes to DNA bases, allowing the automation of DNA sequencing
DNA sequencing
DNA sequencing includes several methods and technologies that are used for determining the order of the nucleotide bases—adenine, guanine, cytosine, and thymine—in a molecule of DNA....
and the examination of the human genome
Human genome
The human genome is the genome of Homo sapiens, which is stored on 23 chromosome pairs plus the small mitochondrial DNA. 22 of the 23 chromosomes are autosomal chromosome pairs, while the remaining pair is sex-determining...
. In Sonogashira's original report of what is now known as the Sonogashira coupling
Sonogashira coupling
In organic chemistry, a Sonogashira coupling is a coupling reaction of terminal alkynes with aryl or vinyl halides. This reaction was first reported by Kenkichi Sonogashira and Nobue Hagihara in 1975.-Catalyst:...
, his group modified an alkyne coupling procedure previously reported by Heck, by adding a copper(I) salt.
Heck's contributions are not limited to the activation of halides by the oxidative addition of palladium. Heck was the first to fully characterize a π-allyl metal complex, and the first to elucidate the mechanism of alkene hydroformylation
Hydroformylation
Hydroformylation, also known as oxo synthesis or oxo process, is an important industrial process for the production of aldehydes from alkenes. This chemical reaction entails the addition of a formyl group and a hydrogen atom to a carbon-carbon double bond...
. Hydroformylation is currently used to produce about 15 billion pound
Pound (mass)
The pound or pound-mass is a unit of mass used in the Imperial, United States customary and other systems of measurement...
s of alcohols and aldehydes each year.
Retirement and honors
Heck retired from the University of Delaware in 1989, where he remains Willis F. Harrington Professor Emeritus in the Department of Chemistry and Biochemistry. Its annual lectureship was named in his honor in 2004. In 2005, he was awarded the Wallace H. Carothers Award, which recognizes creative applications of chemistry that have had substantial commercial impact. He was awarded the 2006 Herbert C. Brown Award for Creative Research in Synthetic Methods. On 6 October 2010, the Swedish Royal Academy of Sciences awarded Heck the Nobel Prize in Chemistry. He shared the 2010 Nobel PrizeNobel Prize
The Nobel Prizes are annual international awards bestowed by Scandinavian committees in recognition of cultural and scientific advances. The will of the Swedish chemist Alfred Nobel, the inventor of dynamite, established the prizes in 1895...
with Ei-ichi Negishi
Ei-ichi Negishi
is a Japanese chemist who has spent most of his career at Purdue University, United States. He is best known for his discovery of the Negishi coupling. He was awarded the 2010 Nobel Prize in Chemistry "for palladium catalyzed cross couplings in organic synthesis" jointly with Richard F. Heck and...
and Akira Suzuki
Akira Suzuki (chemist)
is a Japanese chemist and Nobel Prize Laureate , who first published the Suzuki reaction, the organic reaction of an aryl- or vinyl-boronic acid with an aryl- or vinyl-halide catalyzed by a palladium complex, in 1979.-Life:...
"for palladium-catalyzed cross couplings in organic synthesis." In 2011, Heck was awarded the Glenn T. Seaborg Medal
Glenn T. Seaborg Medal
The Glenn T. Seaborg Medal was first awarded in 1987 by the University of California, Los Angeles , Department of Chemistry and Biochemistry to Nobel prize winning chemist Glenn T. Seaborg, a UCLA alumnus...
for his work on palladium-catalyzed cross couplings.
Richard Heck now resides and intends to retire in the Philippines
Philippines
The Philippines , officially known as the Republic of the Philippines , is a country in Southeast Asia in the western Pacific Ocean. To its north across the Luzon Strait lies Taiwan. West across the South China Sea sits Vietnam...
.
External links
- Department of Chemistry and Biochemistry at the University of DelawareUniversity of DelawareThe university is organized into seven colleges:* College of Agriculture and Natural Resources* College of Arts and Sciences* Alfred Lerner College of Business and Economics* College of Earth, Ocean and Environment* College of Education and Human Development...