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Strategies and Tactics in Organic Synthesis, Vol 6

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Another aspect that probably contributed to the limited interest in the Heck–Matsuda reaction in organic synthesis for many years was the absence of its enantioselective version. In 2012, we described the first enantioselective Heck–Matsuda arylation of olefins using the chiral bisoxazoline 1 as the ligand for this transformation.⁹ This opened the door for the application of this reaction in more challenging transformations such as the enantioselective arylation of acyclic olefins in good yields with enantiocontrol (Scheme 2).¹⁰ Initial studies were carried out aiming at the desymmetrization of cyclic olefins (2), and arylation of more challenging acyclic olefins (4).

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In spite of these advantages, the Heck–Matsuda reaction was overlooked by the chemical community for more than two decades, probably due to the high reactivity of the arenediazonium salts and their potential instability, if possessed of the appropriate counterion. Another reason might be the fact that the extremely successful development of Heck reactions (more specifically arylations) employing aryl halides and aryl triflates, together with the design of a variety of phosphane ligands (chiral and achiral), contributed to the decline of arenediazonium salts as viable starting materials for the Heck arylation. Another important factor that might have retarded the routine use of the Heck–Matsuda in organic synthesis is the incompatibility of most phosphane ligands with arenediazonium salts. Arenediazonium salts tend to react with strong bases and nucleophiles. These limitations also help to explain the late development of the enantioselective version of the Heck–Matsuda reaction, which was achieved only in 2012.

The availability of efficient synthetic methods is a critical aspect in the synthesis of complex organic molecules. After careful planning, the designed synthesis should be achieved in a regio-and stereoselective way, beginning from simple and readily accessible starting materials, if possible under mild reaction conditions.¹ With this objective in mind, we have been working on the development of new methodologies for the short and efficient total synthesis of aryl-containing molecules of pharmacological and functional interest.²

Strategies And Tactics In Organic Synthesis Volume 4

Rather than a simple presentation of data or a secondhand analysis, this classic provides stories that vividly demonstrate the power of the human endeavor known as organic synthesis and the creativity and tenacity of its practitioners.

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The synthetic expertise available in the Smith laboratory has and continues to benefit diverse collaborative projects, by providing access to the design and synthesis of novel analogs and molecular probes. Pleasingly, completed and on-going collaborations have contributed to the development of small-molecule probes for neurodegenerative diseases, bioavailable HIV-1 protease inhibitors, small molecule inhibitors of the HIV cell entry process, and ultra-fast photofragmentation reactions based on s-tertrazene chemistry to serve as phototriggers to initiate conformational changes in peptides on the sub-nanosecond timescale.

Strategies And Tactics In Organic Synthesis Vol 2

This synthetic strategy brings into account interesting aspects of the Heck–Matsuda arylations. As it does not rely on external ligands, the substrates behave as such, not only stabilizing the cationic δ-aryl-palladium complex but also providing structural bias that controls the regio- and stereoselectivity of the overall process. This principle has been an important aspect of many Heck–Matsuda reactions of bi- and multifunctional substrates, as will also be illustrated in the examples below.

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The Smith Group focuses on three principal research areas: (A) development of innovative synthetic methods having wide application; (B) demonstration of the utility of these synthetic tactics for the rapid construction of architecturally complex natural and unnatural products having significant bio-regulatory properties, and (C) novel bioorganic/medicinal chemistry programs, including non-peptide peptidomimetics (i.e., early examples of foldemers) in collaboration with the late Professor Ralph Hirschmann, programs relating to neurodegenerate diseases including Alzhemer’s and tauopathologies, in collaboration with Professors Virginia Lee and John Trojanowski (University of Pennsylvania School of Medicine), studies to inhibit HIV cellular entry (an NIH funded Program Project, involving colleagues at Harvard, Columbia, Bryn Mawr, Drexel, and Johns Hopkins), and projects on peptide/protein folding with Professor Robin Hochstrasser (Penn Chemistry). In each of the collaborative programs, Smith and his students exploit the power of “state-of-the-art” organic synthesis to provide solutions to biomedical programs of importance for the improvement of human health.