People, Trends and Views in Synthetic Organic...

SYNFORMPeople, Trends and Views in Synthetic Organic Chemistry

2013/12

Thieme

SYNSTORIES

Synchronous Ar–F and Ar–SnBond Formation throughFluorostannylation of Arynes

Simple Textiles Become ExcellentCarriers for Organic Catalysts

Nickel-Catalyzed Cross-Couplingof Unactivated Alkyl Halides Using Bis(pinacolato)diboron asReductant

SYNTHESIS/SYNLETT EditorialBoard Focus: Professor TomislavRovis (Colorado State University,Fort Collins, USA)

CONTACT

Your opinion about SYNFORM i

s

welcome, please correspond if

you like:

[email protected]

m

Dow

nloa

ded

by: S

hang

hai U

nive

rsity

. Cop

yrig

hted

mat

eria

l.

Dear readers,

This issue completes the seventh yearof SYNFORM, which was first pub-lished in June 2007. Since then wehave published an awful lot of excit-ing organic chemistry, often from a

rather peculiar perspective, quite different relative to what ispublished in other journalistic-type publications, and defin -itely very different from what can be found in the primaryliterature. We hope you are still finding SYNFORM a usefultool for staying up-to-date with the most recent and excitingresearch developments in organic chemistry, and hopefully apleasant and rewarding reading too. From our side, we guarantee that we will definitely continue to strive to publishhigh quality reports featuring great science from the bestchemists worldwide. Dulcis in fundo, this last 2013 issuepresents a collection of outstanding pieces of research, start-ing from the fluorostannylation of arynes developed byProfessor Yoshida (Japan). Next, we can learn more aboutthe groundbreaking use of textiles as supports for organo -catalysts developed by Professor List and colleagues(Germany). The third SYNSTORY covers a Ni-catalyzedcross-coupling reaction between alkyl halides recently pub-lished by Professor Gong (P. R. of China). The very last article of the year is an Editorial Board Focus on ProfessorRovis (USA).

Enjoy your reading and have a fantastic Christmas time!!

Editor of SYNFORM

SYNFORM A146

IN THIS ISSUE

SYNSTORIES

Synchronous Ar–F and Ar–Sn Bond Formationthrough Fluorostannylation of Arynes . . . . . . . . . . . A147

Simple Textiles Become Excellent Carriers for Organic Catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A150

Nickel-Catalyzed Cross-Coupling of UnactivatedAlkyl Halides Using Bis(pinacolato)diboron asReductant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A153

SYNTHESIS/SYNLETT Editorial Board Focus:Professor Tomislav Rovis (Colorado StateUniversity, Fort Collins, USA) . . . . . . . . . . . . . . . . . . . . . . . . A155

COMING SOON . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A156

SYNFORM, 2013/12Published online: 18.11.2013, DOI: 10.1055/s-0033-1340222

2 0 1 3 © T H I E M E S T U T T G A RT · N E W Y O R K

CONTACT

If you have any questions or wi

sh to send

feedback, please write to Matteo

Zanda at:

[email protected]

Matteo Zanda

Dow

nloa

ded

by: S

hang

hai U

nive

rsity

. Cop

yrig

hted

mat

eria

l.

In view of an increasing demand for convenient and effi-cient methods for synthesizing fluorinated aromatic com-pounds, which are found widely in pharmaceuticals, agro-chemicals, etc., the development of new Ar–F bond-formingreactions has been an important subject in modern syntheticorganic chemistry. Among the diverse aryl fluorides, an effec-tive access to 2-fluoro-biaryl motifs would be of particularimportance, since they constitute a valuable class of biologi-cally active compounds that includes drugs such as brequinar,diflunisal, flurbiprofen, ropion and torezolid (Figure 1).Although a wide variety of aryl fluorides are accessible bypyrolysis of arenediazonium tetrafluoroborates (the Balz–Schiemann reaction), nucleophilic aromatic substitution, elec-trophilic fluorination of aryl Grignard reagents, transition-metal-promoted fluorination and deoxyfluorination of phe-nols, Ar–F bond-forming reactions utilizing arynes, whichhave experienced a marked resurgence of interest as syntheticintermediates in the last decade, remain to be exploited.

Professor Hiroto Yoshida’s group in the Department ofApplied Chemistry, Graduate School of Engineering, at Hiro -shima University (Japan) has been studying aryne insertionreactions into nucleophilic–electrophilic s-bonds (Nu–El)(Bull. Chem. Soc. Jpn. 2010, 83, 199; Synlett 2012, 23,1725), which are triggered by nucleophilic attack of thenucleo philic site to arynes (Scheme 1). Professor Yoshidasaid: “Although a variety of heteroatoms (N, O, P, S, Cl, Se,Br, ...) and even carbon functional groups have been found toserve as the nucleophilic sites, to the best of our knowledgethere has been no precedent for the installation of fluorine intoaromatic rings by the insertion reaction, probably owing tomismatch between fluorine atoms (hard nucleophile) andarynes (soft electrophile).”

“Actually, we have already observed that an F–C bond ofacid fluorides is totally inert toward the insertion reaction ofarynes, being in marked contrast to the facility with acid chlo-rides and bromides (Chem. Commun. 2007, 2405),” con -



SYNSTORIES A147

NEWS AND VIEWS NEWS AND VIEWS NEWS AND VIEWS

Synchronous Ar–F and Ar–Sn Bond Formation throughFluorostannylation of ArynesAngew. Chem. Int. Ed. 2013, 52, 8629–8632

Figure 1

Dow

nloa

ded

by: S

hang

hai U

nive

rsity

. Cop

yrig

hted

mat

eria

l.

http://dx.doi.org/10.1002/anie.201302783http://dx.doi.org/10.1246/bcsj.20090245http://dx.doi.org/10.1055/s-0031-1290401http://dx.doi.org/10.1055/s-0031-1290401http://dx.doi.org/10.1039/B701581J

tinued Professor Yoshida. “In addition, we have neverencountered an example of aryne insertion into an F–Si bondof Me3SiF, generated from 2-(trimethylsilyl)aryl triflate, anaryne precursor, and a fluoride ion.”

In 2004, Professor Yoshida’s group reported on the aryneinsertion into an S–Sn bond of stannyl sulfides (thiostannyla-tion), which enabled Ar–S and Ar–Sn bond-forming processesto occur synchronously at neighboring positions of aromaticrings (Chem. Commun. 2004, 1980), and demonstrated thatan Sn moiety could act as a good electrophilic site in the inser-tion process. During their ongoing studies for expanding thisaryne stannylation by use of stannyl reagents bearing othernucleophilic sites (Nu–Sn), they unexpectedly found that fluorostannylation of arynes took place to give 2-fluoroaryl-stannanes. Professor Yoshida remarked: “Since the fluo-

rostannylation products would be produced by the aryneinsertion into an F–Sn bond of an in situ generated tin fluo-ride (from Nu–Sn species and a fluoride ion used as an arynegenerator), we naturally examined the reaction of arynes witha tin fluoride, and it worked very well!”

As outlined in Scheme 2, diverse 2-fluoroarylstannanescould be synthesized straightforwardly in high yield by sim-ply mixing 2-(trimethylsilyl)aryl triflates, tributyltin fluorideand a fluoride ion. Perfect regioselectivities were observed inthe reaction of 3-methoxybenzyne, 3-bromobenzyne or 3-chlorobenzyne, where fluorine was incorporated into the metapositions of the substituents, showing that the fluorine indeedacts as a nucleophilic site in the fluorostannylation. It shouldbe noted that the TMS moiety of 4-(trimethylsilyl)benzyneremained intact throughout the reaction regardless of the exis-



SYNSTORIES A148

Scheme 1

Scheme 2

Dow

nloa

ded

by: S

hang

hai U

nive

rsity

. Cop

yrig

hted

mat

eria

l.

http://dx.doi.org/10.1039/B405883F

tence of a fluoride ion, leading to the selective formation oftributyl[2-fluoro-4-(trimethylsilyl)phenyl]stannane.

“In marked contrast to the results above, the reaction of anaryne generated by oxidation of 1-aminobenzotriazole withPb(OAc)4 did not give the fluorostannylation product at all,implying that the presence of a fluoride ion is indispensablefor the fluorostannylation to proceed,” explained ProfessorYoshida. “Hence, we propose a pathway involving the gener-ation of difluorotributylstannate (Bu3SnF2–) from Bu3SnF anda fluoride ion (Scheme 3). Subsequent insertion of an aryneinto an F–Sn bond via intermediate A, followed by release ofa fluoride ion from intermediate B, provides a product.”

This study represented the first aryne insertion reactioninto a fluorine-containing s-bond that produced various 2-fluo roarylstannanes, which are versatile synthetic interme-diates that can be converted into 2-fluorobiaryls of pharma -cological importance by the Migita–Kosugi–Stille reaction.Furthermore, the study demonstrated that the hard/soft mis-match between fluorine atoms and arynes could be overcomeby choosing a suitable electrophilic site in s-bond com-pounds. The combined use of a tin fluoride and a fluoride ionis also a key to the successful fluorostannylation. ProfessorYoshida concluded: “The present findings will undoubtedlytrigger further development of new Ar–F bond-forming reac-tions utilizing arynes, and we are also continuing the researchon this topic, of course.”



SYNSTORIES A149

Matteo Zanda

Scheme 3

About the authors

Hiroto Yoshida was born in Fukuoka(Japan) in 1973. He graduated fromKyoto University (Japan) in 1996 andreceived his Ph.D. from Kyoto Uni -versity under the supervision of Pro -fessors Eiji Shirakawa and TamejiroHiyama in 2001. He then became anAssistant Professor at HiroshimaUniversity (Japan) in 2001 and waspromoted to an Associate Professorin 2006. He received the BCSJ Award(2001), the Japan Combinatorial

Chemistry Focus Group Award in Synthetic Organic Chemistry,Japan (2005), the Tetrahedron Letters Most Cited Paper 2003–2006 Award (2006), The Chemical Society of Japan Award forYoung Chemists (2007), The Society of Silicon Chemistry Awardfor Young Chemists (2008), and The Young Scientists’ Prize,The Commendation for Science and Technology by the Ministerof Education, Culture, Sports, Science and Technology (2009).His research interests include the development of new syntheticmethods by use of reactive intermediates and/or transition-metal catalysts.

Prof. H. Yoshida

Dow

nloa

ded

by: S

hang

hai U

nive

rsity

. Cop

yrig

hted

mat

eria

l.

Organic catalysts represent a relatively new class of catal -ysts that have a rapidly growing impact on the synthesis ofcomplex and high-value pharmaceuticals and fine chemicals –also due to the fundamental contributions of ProfessorBenjamin List from the Max-Planck-Institut für Kohlen -forschung (MPI Kofo) in Mülheim an der Ruhr (Germany),who has developed basic concepts to chemical synthesisincluding aminocatalysis, enamine catalysis, and asymmetric-counter-anion-directed catalysis (ACDC, Angew. Chem. Int.Ed. 2006, 45, 4193).

The List group has pioneered several new amine- andamino acid-catalyzed asymmetric reactions originating fromList’s discovery of the proline-catalyzed direct asymmetricintermolecular aldol reaction in 2000. Shortly thereafter, thegroup developed the concept of enamine catalysis and intro-duced the first proline-catalyzed asymmetric Mannich reac-tion. Subsequently, they pioneered novel Michael reactions,a-aminations, enol-exo-aldolizations, and aldehyde a-alkyla-tions. Furthermore, collaborative efforts involving the Listgroup have provided a clearer mechanistic understanding ofenamine catalysis and established the basis for the design ofnew reactions and catalysts. In particular, the very generalACDC strategy for asymmetric synthesis has recently foundwidespread use in organocatalysis, transition-metal catalysis,and Lewis acid catalysis.

So far, the industrial use of organic catalysts has been hin-dered by the lack of effective and inexpensive techniques forthe immobilization on certain carrier materials to use themrepeatedly or even continuously without complicated, expen-sive separation and recovery processes. Now, the high-impactjournal Science has published parts of an ongoing Germanresearch project funded by resources from the FederalMinistry of Economics suggesting a simple but groundbreak-ing solution.

An international team working with chemists from theDeutsches Textilforschungszentrum Nord-West (DTNW) inKrefeld (Germany), the Max-Planck-Institut für Kohlen for -schung (MPI Kofo) in Mülheim an der Ruhr (Germany) andSungkyunkwan University in Suwon (Korea) has developedan innovative process for the durable fixation of organic catal -ysts on a simple nylon fabric typically known from ladiestights. With the help of monochromatic ultraviolet light (222nm), the catalysts can be easily grafted onto the fiber’s sur-face. The fabric thereby acts as a support for the substances onwhich a chemical reaction occurs.

The textile experts from DTNW, Thomas Mayer-Gall andKlaus Opwis, explain that up until now, science has focusedmore on the macroscopic functionality of textiles, for exampleclothing. “In contrast to this, our method can give simple tex-tiles microscopic functionalities,” added the Korean chemist



Simple Textiles Become Excellent Carriers for OrganicCatalystsScience 2013, 341, 1225–1229

SYNSTORIES A150

Figure 1 Chemical structures of immobilized organic catalysts

Dow

nloa

ded

by: S

hang

hai U

nive

rsity

. Cop

yrig

hted

mat

eria

l.

http://dx.doi.org/10.1126/science.1242196http://dx.doi.org/10.1002/anie.200600512http://dx.doi.org/10.1002/anie.200600512

Ji-Woong Lee, who recently completed his Ph.D. at the MPIKofo under the supervision of Professor Benjamin List.

To prove their concept, the DTNW scientists immobilizedthree organic catalysts provided by Professor List’s group: abase (dimethylaminopyridine, DMAP), a sulfonic acid and acatalyst that functions as both an acid and a base (Figure 1).

Afterwards, Ji-Woong Lee carried out several hundred testruns for various enantioselective reactions. All three catalystsconverted around 90 percent of the source materials into thedesired products. In particular, the textile-fixed acid/base chi-ral catalyst shows an amazing performance with regard to cat-alytic activity, enantioselectivity and recyclability. For exam-ple, the enantioselective desymmetrization of cyclic anhy-drides runs for more than 250 cycles, without any significantloss of its catalytic activity, while providing an impressiveenantiomeric ratio of 96.5:3.5 (Figure 2). “This is a remark-ably high number and far better than what we expected at thebeginning of our work,” project leader Klaus Opwis fromDTNW explains, “especially with regard to the negligible lowprice of the textile compared to conventional carrier materialsfor catalysts, the simple processing and the inherent advan-tages of fibrous materials such as flexibility, mechanicalstrength and high surface area!”

“We are pretty confident that this new organotextile catal-ysis is able to open the door for manifold new applications inpharmaceuticals, fine chemicals, biochemistry and materialsscience,” Professor List added. “In the future, it will be mucheasier to produce some active pharmaceutical substances andchemical compounds than was the case to date.” The catalyst-loaded textiles can be used for various syntheses of industrial

relevance. For instance, one of the immobilized catalysts thatthe researchers used in this way plays an important role in thesynthesis of valuable precursors of statin derivatives, whichcould only be used previously in dissolved form, making theproduction process very complicated and expensive.Immobilizing this catalyst on fabric simplifies productionconsiderably.

Moreover, this process may be expected to yield similaradvantages for other chemical processes or even non-typicallychemical applications such as the treatment of water in loca-tions where people are cut off from the water supply. “Ourtextile carrier nylon is flexible and very inexpensive. Dry tex-tiles loaded with catalysts are easy to transport, which meansthat it is simpler to meet the requirements for some chemicalprocesses where it is practically impossible to set up sophisti-cated chemical systems. In addition, the photochemicalmethod enables the low-cost production of long-term func-tionalized textiles without causing any pollution,” theresearch team summarizes. “Our future work foresees theextension of our smart approach to other catalytic systems notexplicitly limited to applications in chemical syntheses.”



SYNSTORIES A151

Figure 2 Enantioselective desymmetrization of cyclic anhydrides witha textile-fixed chinchona-sulfonamide organocatalyst

About the authors

Ji-Woong Lee received his M.Sc. in chemistry from SungkyunkwanUniversity (Korea) in 2009 under theguidance of Professor Choong EuiSong. Afterwards, he moved to Max‐Planck‐Institut für Kohlen forschung(Mülheim an der Ruhr, Germany),where he recently finished his Ph.D. inorganic chemistry (Magna cum laude)in the group of Professor BenjaminList. Today, he is a postdoctoral fellowat Sungkyunkwan University. His main

interests are in the field of unconventional asymmetric hetero-geneous and homogeneous organocatalysis. He has receivedmany awards, honors and scholarships, including a Brain Korea21 Scholarship (Sungkyunkwan University, Graduate School), a Best Publication Award (Center for Intelligent NanoBio‐Mate -rials, Ihwa Womans University, Department of Chemistry) and a Promotionsstipendium of the Max‐Planck‐Institut für Kohlen -forschung. In addition, he was a contributor to Synfacts(Ed. B. List) in 2009.

Dr. J.-W. Lee

Matteo Zanda

Dow

nloa

ded

by: S

hang

hai U

nive

rsity

. Cop

yrig

hted

mat

eria

l.



SYNSTORIES A152

Thomas Mayer-Gall graduated inorganometallic chemistry at the Uni -versity of Bochum (Germany). At present, he is a member of the scien-tific staff of the Deutsches Textilfor -schungs zentrum Nord-West (DTNW)located in Krefeld (Germany) and ofthe working group of ProfessorJochen S. Gutmann at the Universityof Duisburg-Essen (Germany). Hismain interests are in the field of newfunctional adsorbing textiles and cata-

lytic active surfaces/textiles. Together with Klaus Opwis hedeveloped the first textile-fixed organometallic catalyst in 2007.Recently, he started working on metal-adsorbing textile sur -faces for the recovery of noble metals and on new heteroge -neous asymmetric catalysts.

Klaus Opwis received his diploma inchemistry from Duisburg University(Germany) in 1996. Afterwards, hemoved to Deutsches Textilforschungs -zentrum Nord-West. In his Ph.D. the-sis (University Duisburg-Essen, 2003)he described the concept for theimmobilization of catalysts on textilematerials for the first time. Since 2007he is the head of the working group“Biotechnology & Catalysis” at DTNW.Besides textile-fixed catalysts, his

research interests include enzymatic processes in textile finish -ing, biopolymers, modifications in supercritical carbon dioxideand ionic liquids, flexible textile-based solar cells, photochemi-cal surface modifications of synthetic polymers, conductive tex-tiles and flame-retardant finishing of textiles.

Choong Eui Song, born in 1955,has been a full Professor at Sung -kyunkwan University (Korea) since2004. He received his B.Sc. in 1980from Chungang University (Korea) andobtained a Diploma (1985) and aPh.D. (1988) at RWTH Aachen(Germany). After completing his Ph.D.he worked as a Principal ResearchScientist at the Korea Institute ofScience and Technology (KIST). In2001, he was appointed as Head of

the National Research Laboratory for Green Chirotechnology inKorea. In 2004, he moved to his current position and in 2006he was appointed as a Director at the Research Institute of

Advanced Nanomaterials and Institute of Basic Sciences atSungkyunkwan University. His research interests focus onasymmetric catalysis, ionic-liquid chemistry and nanochemistry.He received the Scientist of the Month Award from the Ministryof Science and Technology in Korea (2001).

Jochen S. Gutmann studied chemi-stry at the Technische HochschuleDarmstadt (Germany) and the Uni -versity of Bristol (UK). He received hisPh.D. from the University of Mainz(Germany) and worked as a postdoc-toral fellow at the IPF Dresden(Germany) and Cornell University(USA). In 2002, he joined the MPI forPolymer Research and was appointedas a Professor for Physical Chemistryat the University Mainz in 2005. Since

2010 he is a Professor for Physical Chemistry at the Universityof Duisburg-Essen (Germany) and the Managing Director of theDTNW in Krefeld. His research focuses on the characterizationof multicomponent polymer materials and chemistry at inter-faces.

Benjamin List is currently theManaging Director of the Max-Planck-Institut für Kohlenforschung inMülheim an der Ruhr. He has been aDirector there since 2005. He obtai-ned his Ph.D. in 1997 at the Johann-Wolfgang-Goethe-University inFrankfurt am Main (Germany). From1997 until 1998 he conducted post-doctoral research at The ScrippsResearch Institute in La Jolla (USA)and became an Assistant Professor

there in January 1999. In 2003, he joined the Max-Planck-Institut für Kohlenforschung in Mülheim. He has been an hono-rary professor at the University of Cologne (Germany) since2004. Professor List’s research focuses on organic synthesisand catalysis. He has contributed fundamental concepts tochemical synthesis including aminocatalysis, enamine catalysis,and asymmetric-counter-anion-directed catalysis (ACDC). Hislatest work deals with chiral anions in asymmetric catalysis. Hehas received many honors and awards, including the 2003 CarlDuisberg Memorial Award, the 2004 Degussa Prize for ChiralChemistry, the 2004 Lieseberg Prize of the University ofHeidelberg, the 2005 Novartis Young Investigator Award, the2007 AstraZeneca Research Award in Organic Chemistry, andthe 2012 Otto Bayer Award. Very recently, he obtained the2013 Mukaiyama Award.

Dr. T. Mayer-Gall

Dr. K. Opwis

Prof. C. E. Song

Prof. J. S. Gutmann

Prof. B. List

Dow

nloa

ded

by: S

hang

hai U

nive

rsity

. Cop

yrig

hted

mat

eria

l.

A fundamental issue in organic synthesis is selectivity.Conventional catalytic cross-coupling methods take advan-tage of reactions between a nucleophile, such as an organo -metallic species, and an electrophile, for example an alkylhalide or a Michael acceptor, in the presence of a transition-metal catalyst. However, coupling of two structurally andelectronically similar electrophiles, such as two alkyl halides,suffers a severe selectivity issue. For instance, the Ullmanreac tion, discovered in 1901, is generally limited to homo-couplings. The coupling of alkyl halides to form a newC(sp3)–C(sp3) bond is particularly challenging due to slowoxidative addition and possible b-elimination problems.

Professor Hegui Gong from the Department of Chemistry,Shanghai University (P. R. of China) remarked: “When I start-ed my independent career in late 2008, I was fascinated withdeveloping a convenient approach to the construction ofC(sp3)–C(sp3) bonds that did not need preparation of organo -metallic reagents such as Grignards and organozincs. Webelieved this could significantly reduce the laborious opera-tions involved in this process, and might lead to new reaction

mechanisms that differ from the conventional coupl ing reac-tions.” Inspired by the Ni-catalyzed Negishi coupling ofalkylzincs with alkyl halides, pioneered by Knochel and Fu,Professor Gong’s group initiated their first attempt by mixingtwo different alkyl halides in the presence of zinc powder andcatalytic amounts of a Ni/pybox ligand. This strategy effi-ciently provided alkyl–alkyl compounds in moderate to goodyields with excellent functional group tolerance; however, oneof the coupling halides was required in excess (3 equiv). Thehighly competitive homo-coupling side reaction was prob-lematic, suggesting that the Ni/Zn reductive conditions couldnot effectively bias the two alkyl coupling partners (Org. Lett.2011, 13, 2138).

“In order to promote the chemoselectivity of the Ni-cat-alytic conditions, we turned our attention to boron reduc-tants,” said Professor Gong. “We anticipated that a possibleNi–B complex might differentiate the two alkyl halides’oxidative coupling stage by taking advantage of subtle elec-tronic and steric differences in the two alkyl partners. Aftertremendous effort, my co-worker Hailiang Xu eventually dis-



Nickel-Catalyzed Cross-Coupling of Unactivated AlkylHalides Using Bis(pinacolato)diboron as ReductantChem. Sci. 2013, 4, 4022–4029

SYNSTORIES A153

Dow

nloa

ded

by: S

hang

hai U

nive

rsity

. Cop

yrig

hted

mat

eria

l.

http://dx.doi.org/10.1039/C3SC51098Khttp://dx.doi.org/10.1021/ol200617fhttp://dx.doi.org/10.1021/ol200617f

covered that (Bpin)2 serves this purpose.” The reactionrequires only 1.5 equivalents of the second alkyl halides,which works quite well for the coupling of secondary as wellas hindered primary halides with primary bromides. In mostcases, the results were good in comparison to the conventionalNi-catalyzed Suzuki reactions. “To the best of our knowledge,this work should represent the first efficient coupling of unac-tivated alkyl halides using boron as the terminal reductant,”

remarked Professor Gong. Preliminary mechanistic studiessuggest that an in situ organoboron/Suzuki process is not pos-sible. Professor Gong concluded: “Although the details of themechanism are still not clear, we believe double oxidativeadditions of alkyl halides to Ni are operative.”



About the authors

Hegui Gong was born in 1974. Hereceived a bachelor’s degree in 1995from Zhengzhou University of LightIndustry and a Master’s degree fromTsinghua University in 1998 (both P.R. of China). In 2005 he obtained hisPh.D. degree from the University ofTexas at Austin (USA) under thesupervision of Professor MichaelKrische. After postdoctoral researchat the University of North Carolina atChapel Hill in Professor Michel

Gagné’s laboratories, he was appointed as a Full Professor atShanghai University (P. R. of China) in 2008. His research focu-ses on two general areas of organic chemistry: supramolecularchemistry and organic synthesis.

Hailiang Xu was born in 1986 inHebei province (P. R. of China). He was awarded a bachelor’s degreefrom Huazhong Agricultural Universityin 2010 and a Master’s degree fromShanghai University in 2013 (both P.R. of China) under the guidance ofProfessor Hegui Gong, where he worked on the Ni-catalyzed reductivecross-coupling of unactivated alkylhalides. He is currently a researchassistant at City University of HongKong (P. R. of China) with ProfessorPeggy Lo.

Chenglong Zhao was born in 1988in Xian, Shanxi province (P. R. ofChina). He received a bachelor’sdegree in Chemistry from Northwest A & F University (P. R. of China) in2011. Presently, he is enrolled in thechemistry Master’s program at Shang -hai University under the supervision ofProfessor Hegui Gong. His thesisresearch involves the reductive coupl -ing of alkyl halides with acids. Prof. H. Gong

H. Xu

C. Zhao

SYNSTORIES A154

Matteo Zanda

Dow

nloa

ded

by: S

hang

hai U

nive

rsity

. Cop

yrig

hted

mat

eria

l.



SYNSTORIES A155

Background and Purpose. SYNFORM will from timeto time portrait SYNTHESIS/SYNLETT Editorial and AdvisoryBoard members who answer several questions regarding theirresearch interests and revealing their impressions and viewson the developments in organic chemistry as a generalresearch field. In this issue, we present Professor TomislavRovis from Colorado State University in Fort Collins, USA.

INTERVIEWSYNFORM What are your main current research interests?

Prof. T. Rovis We continue to be enamored with the possi-bilities that N-heterocyclic carbenes (NHCs) afford for novelbond disconnections. We are also actively engaged in Rh-catalyzed C–H activations, particularly as a route to nitro-gen heterocycles. Last, and most recent, in collaborationwith Tom Ward at Basel we are pursuing the development ofartificial metalloenzymes for organic synthesis.

SYNFORM What is your most important scientificachieve ment to date and why?

Prof. T. Rovis If one limits that question to achievementsdone some time ago, so that the achievement can be anal -yzed in the context of some history, it would have to be theintroduction and development of aminoindanol-derived chi-ral triazolinylidine carbenes. These catalysts and the umpol-ung reactivity they enable have caught people’s imagination.We were lucky to be there early on.

SYNFORM Do you have hobbies, besides chemistry?

Prof. T. Rovis Skiing, basketball, golf, wine.

SYNFORM What is the main goal in your scientificcareer?

Prof. T. Rovis The training of the next generation of scien-tists, to think clearly, deeply and critically about the worldaround them. Of course, science would not move forward ifthis were the only thing we did. It is also important to edu-cate the community about a new way to think about a givenproblem. That’s also a major goal.

SYNTHESIS/SYNLETT Editorial Board Focus: ProfessorTomislav Rovis (Colorado State University, Fort Collins, USA)

BIOGRAPHICAL SKETCHTomislav Rovis was born inZagreb in former Yugoslavia butwas largely raised in southernOntario, Canada. Following hisundergraduate studies at theUniversity of Toronto (Canada), heearned his Ph.D. degree at thesame institution in 1998 under thedirection of Professor MarkLautens. From 1998–2000, hewas an NSERC PostdoctoralFellow at Harvard University (USA)

with Professor David A. Evans. In 2000, he began his in -dependent career at Colorado State University and was pro-moted in 2005 to Associate Professor and in 2008 to Pro -fessor. His group’s accomplishments have been recognizedby a number of awards including an Arthur C. Cope Scholarand an NSF CAREER Award. He has been named aGlaxoSmithKline Scholar, Amgen Young Investigator, Eli LillyGrantee, Alfred P. Sloan Fellow, a Monfort Professor atColorado State University, Roche Excellence in ChemistryAwardee, a Fellow of the American Association for theAdvancement of Science and a Katritzky Young Investigatorin Heterocyclic Chemistry. He currently holds the John K.Stille Chair in Chemistry.

Prof. T. Rovis

Matteo Zanda

Dow

nloa

ded

by: S

hang

hai U

nive

rsity

. Cop

yrig

hted

mat

eria

l.

COMING SOON COMING SOON

SYNFORM 2014/01is available from December 13, 2013In the next issues:

SYNSTORIES

Stereoinversion of Tertiary Alcohols to Tertiary-Alkyl Isonitrilesand Amines(Focus on an article from the current literature)

Efficient Synthesis of Functionalized Unsymmetrical DialkylTrisulfanes(Focus on an article from the current literature)

SYNFORM

CONTACTMatteo Zanda,NRP Chair in Medical TechnologiesInstitute of Medical SciencesUniversity of AberdeenForesterhill, Aberdeen, AB25 2ZD, UKand C.N.R. – Istituto di Chimica del Riconoscimento Molecolare,Via Mancinelli, 7, 20131 Milano, Italy,e-mail: [email protected], fax: +39 02 23993080

FURTHER HIGHLIGHTSSYNTHESISReview on: Direct Carboxylative Reactions for the Trans -for ma tion of Carbon Dioxide into Carboxylic Acids andDerivatives(by X. Cai and B. Xie)

SYNLETTAccount on: Site-Selective Heterofunctionalization ofCyclodextrins: Discovery, Development, and Use in Catalysis(by M. Sollogoub)

SYNFACTSSynfact of the Month in category “Metal-Mediated Synthesis”:Fluorination of Aryl Trifluoroborates

EditorMatteo Zanda, NRP Chair in Medical Technologies, Institute of MedicalSciences, University of Aberdeen, Foresterhill, Aberdeen, AB25 2ZD, UKand C.N.R. – Istituto di Chimica del Riconoscimento MolecolareVia Mancinelli, 7, 20131 Milano, ItalyEditorial Assistant: Alison M. [email protected]; fax: +39 02 23993080

Editorial OfficeManaging Editor: Susanne Haak,[email protected], phone: +49 711 8931 786Scientific Editor: Selena Boothroyd,[email protected] Scientific Editor: Michael Binanzer,[email protected], phone: +49 711 8931 768Senior Production Editor: Thomas Loop,[email protected], phone: +49 711 8931 778Production Editor: Helene Deufel,[email protected], phone: +49 711 8931 929Production Editor: Thorsten Schön,[email protected], phone: +49 711 8931 781Editorial Assistant: Sabine Heller,[email protected], phone: +49 711 8931 744Marketing Manager: Julia Stötzner,[email protected], phone: +49 711 8931 771Postal Address: SYNTHESIS/SYNLETT/SYNFACTS, Editorial Office,Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany, Homepage: www.thieme-chemistry.com

Publication InformationSYNFORM will be published 12 times in 2013 by Georg Thieme VerlagKG, Rüdigerstraße 14, 70469 Stuttgart, Germany, and is an additionalonline service for SYNTHESIS, SYNLETT and SYNFACTS.

Publication PolicyProduct names which are in fact registered trademarks may not have beenspecifically designated as such in every case. Thus, in those cases where aproduct has been referred to by its registered trademark it cannot be conclu-ded that the name used is public domain. The same applies as regardspatents or registered designs.

Ordering Information for Print Subscriptions to SYNTHESIS,SYNLETT and SYNFACTSThe Americas: Thieme Publishers New York, Thieme Medical Publishers,Inc., 333 Seventh Avenue, New York, NY 10001, USA. To order: [email protected] or use the Web site facilities atwww.thieme-chemistry.com, phone: +1 212 760 0888Order toll-free within the USA: +1 800 782 3488Fax: +1 212 947 1112

Airfreight and mailing in the USA by Publications Expediters Inc., 200 Meacham Ave., Elmont NY 11003. Periodicals postage paid at JamaicaNY 11431.

Europe, Africa, Asia, and Australia: Thieme Publishers Stuttgart, GeorgThieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany. To order: [email protected] or use the Web site facilities atwww.thieme-chemistry.com.Phone: +49 711 8931 421; Fax: +49 711 8931 410

Current list prices are available through www.thieme-chemistry.com.

Online AccessThe online versions of SYNFORM as well SYNTHESIS, SYNLETT andSYNFACTS are available through Thieme-connect (www.thieme-connect.com/ejournals) where you may also register for free trial accounts.For information on multi-site licenses and pricing for corporate customersas well as backfiles please contact our regional offices:

The Americas: [email protected], phone: +1 212 584 4695

Europe, Africa, Asia, and Australia: [email protected], phone: +49 711 8931 407

India: [email protected], phone +91 120 45 56 600

Japan: [email protected], phone +81 3 3358 0692

Manuscript Submission to SYNTHESIS and SYNLETTPlease consult the Instructions for Authors before compiling a new manu-script. The current version and the Word template for manuscript prepara -tion are available for download at www.thieme-chemistry.com. Use of theWord template helps to speed up the refereeing and production process.

CopyrightThis publication, including all individual contributions and illustrations pub -lished therein, is legally protected by copyright for the duration of the copy-right period. Any use, exploitation or commercialization outside the narrowlimits set by copyright legislation, without the publisher’s consent, is illegaland liable to criminal prosecution. This applies translating, copying and re production in printed or electronic media forms (databases, online net-work systems, Internet, broadcasting, telecasting, CD-ROM, hard disk stora-ge, microcopy edition, photomechanical and other reproduction methods) aswell as making the material accessible to users of such media (e.g., asonline or offline backfiles).

Copyright Permission for Users in the USAAuthorization to photocopy items for internal or personal use, or the inter nalor personal use of specific clients, is granted by Georg Thieme Verlag KGStuttgart · New York for libraries and other users registered with the Copy -right Clearance Center (CCC) Transactional Reporting Service, providedthat the base fee of US$ 25.00 per copy of each article is paid directly toCCC, 22 Rosewood Drive, Danvers, MA 01923, USA, 0341-0501/02.

Dow

nloa

ded

by: S

hang

hai U

nive

rsity

. Cop

yrig

hted

mat

eria

l.
http://dx.doi.org/10.1055/s-0033-1340140

People, Trends and Views in Synthetic Organic...

Documents

Transcript of People, Trends and Views in Synthetic Organic...