SYNFORM is available as part of the online editions of SYNTHESIS, SYNLETT and SYNFACTS through Thieme eJournals. This supplementary feature is available free of charge. SYNFORM presents people, trends, and views in synthetic organic chemistry with direct links to all quoted original papers. To view or download issues of SYNFORM, please click here.
Today is the last day of the year. I know this Editorial will be published in the February issue of SYNFORM, nevertheless, I can’t pretend today is a different day: it’s December 31st, 2011 and most of us are ready to celebrate the looming New Year with family and friends. I found a quote on the web, which reflects pretty well what’s going to happen tonight: “An optimist stays up until midnight to see the New Year in. A pessimist stays up to make sure the old year leaves” (Bill Vaughn). I think for most of us this was a mixed year, something was good and something was bad. However, for our beloved art and science of organic chemistry, this was definitely a great year in terms of research achievements and progress, whereas it was less good in terms of funding, at least in Europe, mainly (but not exclusively) because of the globally difficult economic situation. Personally, my commitment for the New Year is to focus the research of my group even more on some of the most important, unmet medical needs, where organic chemistry plays a key role. But certainly organic chemistry will continue to play a pivotal role in many other areas such as preserving our environment, producing and storing energy in more efficient ways, creating smarter materials. I wish to all of You, Dear Readers, a fantastic and productive Year 2012, full of great results and exciting science! This said; let’s have a closer look at the content of this issue. The first SYNSTORY reports on a very original and exciting discovery by the group of Professor C. W. Bielawski (USA): the “retro-click” reaction, i.e. how to use mechanical force to achieve an unprecedented 1,2,3-triazole cycloreversion. The second SYNSTORY reveals how the group of Professor M. Nakamura (Japan) was able to tune the chemoselectivity in iron-catalyzed Sonogashira-type reactions, achieving a selective alkynylation of non-activated alkyl halides (chlorides, bromides and iodides). The issue is completed by the Young Career Focus on Dr. U. Schneider (UK).
The copper-catalyzed 1,3-dipolar cycloaddition of azide and alkyne moieties, which allows access to 1,4-disubstituted 1,2,3-triazoles, has found broad applicability over the past decade due to its rapid kinetics under mild conditions, high functional group and solvent tolerance, good atom economy, and the relative chemical inertness and thermal stability of the products. In addition to finding utility in molecular and polymer functionalizations, this motif has been applied to robust, chemically orthogonal ligations for the study of biological systems. Indeed, the triazole products are so stable that no simple chemical or thermal treatment capable of cleanly reverting these moieties into their constituent azides and alkynes was known. Recently, the group of Professor Christopher W. Bielawski from the University of Texas at Austin (USA) envisioned that mechanical force could be used to surmount the otherwise inaccessible barrier to triazole cycloreversion. The researchers found that embedding a 1,2,3-triazole within a poly(methyl acrylate) chain renders it susceptible to a cycloreversion induced by ultrasound.
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The formation of novel carbon–carbon bonds through catalytic reactions involving non-activated substrates represents a very hot area of research, undergoing rapid evolution. The use of rather inert alkyl halides as substrates in metal-catalyzed C–C bond-forming reactions is particularly attractive. Recently, the group of Professor Masaharu Nakamura from Kyoto University (Japan) reported a new process catalyzed by a bisphosphine–iron(II) complex which leads to the formation of a new Csp–Csp3 bond between non-activated alkyl halides (chlorides, bromides and iodides) and terminal alkynes. The reaction is remarkably efficient and takes place both with primary and secondary alkyl halides.
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Background and Purpose. SYNFORM will from time to time meet young up-and-coming researchers who are performing exceptionally well in the arena of organic chemistry and related fields of research, in order to introduce them to the readership. This SYNSTORY with a Young Career Focus presents Dr. Uwe Schneider, University of Edinburgh, UK.
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Administration, Teaching and Research: not necessarily in order of preference, but these are the three benchmarks of our academic profession. I am pretty sure that most of us strive to reduce the first in order to maxi mize the time that can be dedicated to the other two. And some of us, including myself, are lucky enough to have not too much of the second (but please don’t tell to the senior management of my college...), and more time for the real fun in our fantastic profession: research! I am not saying that teaching is not rewarding, it definitely is. And I am not saying it is not very useful, not just to the students I mean: it definitely is! But most of you will agree, I am sure, that nothing is as exciting as research! I really believe that one could live one thousand years, or more, and remain in love with research like the very first day. I think you will admit that is not always like that! And I would bet any money that passion for research was the dominant driving force for the scientists whose work is presented in this issue of SYNFORM. In the first SYNSTORY, Professor M. P. Watson (USA) explains how her group was able to develop an enantioselective copper(I)-catalyzed addition of terminal alkynes to isochroman acetals, which can be used to prepare chiral benzopyrans in high enantioselectivities and yields. The second SYNSTORY is focused on the work of Professor E. J. Alexanian (USA) and his new methodology for achieving a formal vicinal dioxygenation of terminal alkenes using a strikingly simple metal-free radical process. The issue is completed by an Editorial Advisory Board Profile on Professor C. Bolm (Germany).
The enantioselective addition of terminal alkynes to aldehydes and ketones is a well-established and powerful syn - thetic methodology that provides an effective entry to chiral propargyl alcohols in high enantiomeric purity (J. Am. Chem. Soc. 2011, 133, 1286 and references therein). In contrast, the enantioselective alkynylation of oxocarbenium ions is comparatively much less developed and this is particularly true for oxocarbenium ions derived from isochroman acetals, because their alkynylation would produce biologically important scaffolds belonging to the class of chiral substituted benzopyrans. Recently, the group of Professor Mary P. Watson from the University of Delaware (Newark, USA) reported an important breakthrough in the field: an enantioselective TMSOTf-promoted copper(I)-catalyzed addition of terminal alkynes to isochroman acetals, which can be used to prepare chiral benzopyrans in high enantioselectivities and yields. The reaction makes use of chiral oxazoline catalysts and has a significantly broad scope.
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Alkene difunctionalizations are an important class of reactions that incorporate vicinal heteroatomic functionality in simple alkene substrates. However, current methods for alkene difunctionalization rely on the use of highly toxic and/or expensive transition-metal catalysts (e.g., osmium), which is a major drawback to the use of these methods in organic synthesis. Recently, the group of Professor Erik J. Alexanian from the University of North Carolina at Chapel Hill (USA) reported a new methodology for achieving a formal vicinal dioxygenation of terminal alkenes using a strikingly simple metalfree radical process relying on the use of oxygen as an oxidant, dilauroyl peroxide as initiator, and simple hydroxamic acid derivatives as reagents.
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Background and Purpose. SYNFORM will from time to time portrait SYNTHESIS/SYNLETT Advisory Board members who answer several questions regarding their research interests and revealing their impressions and views on the developments in organic chemistry as a general research field. In this issue, we present Professor Carsten Bolm, RWTH Aachen University (Germany).
To read more please download SYNFORM 2012/01 online, free of charge.
I would like to take advantage of this editorial to emphasize the importance of your input to the selection of articles to be published in SYNFORM. Normally, top quality articles are selected by me following a thorough screening of the current literature, or (less often) are suggested by the Thieme Chemistry Editorial Board members. However, at SYNFORM we believe that You, our Readers, could assume the role of protagonists in the selection process, by suggesting high impact articles from the very recent literature that you would like to see featured in SYNFORM, including your own papers of course. This is also true for topics of current great interest that you would like to see covered and discussed in INSIDE STORIES, or protagonists of organic chemistry that you would like to see in our Young Career Profiles or in ad hoc INSIDE STORIES like the interview to Sir Jack Baldwin that was published in issue 01/2008. We would be delighted to get your suggestions and inputs at synform@chem.polimi.it and we believe that this would make SYNFORM even more rich and interesting. This new issue of SYNFORM is in my humble opinion one of the best ever, as it features an outstanding contribution by the group of the Nobel Laureate Professor E. J. Corey (USA) on a novel and highly useful silicon protecting group, and another very exciting piece of research from the group of Professor T. Ritter (USA) about the development of a new methodology for the introduction of the OCF3 group onto aryl stannanes and boronic acids. The issue is completed by an Advisory Board Focus on Professor A. B. Charette (Canada).
The trifluoromethoxy group is commonly encountered as a substituent of aromatic groups in drugs and bioactive molecules, but few synthetic methods are available to incorporate this function in organic molecules. Recently, the group of Professor Tobias Ritter from Harvard University (Cambridge, Massachusetts, USA) reported a new methodology for the synthesis of trifluoromethoxy arenes based on a cross-coupling reaction of both aryl stannanes and arylboronic acids. The reaction leads to the formation of a new Caryl–OCF3 bond and is mediated by silver.
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