New interesting molecular topologies by way of modern cross-coupling reactions

Meijere, Armin de; Stulgies, Baldur; Albrecht, K.; Rauch, Karsten; Wegner, Hermann A.; Hopf, Henning; Scott, Lawrence T.; Eshdat, Lior; Aprahamian, Ivan; Rabinovitz, Mordecai

doi:10.1351/pac200678040813

Cited by 28 publications

(14 citation statements)

References 2 publications

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“…In particular,t he development of synthetic methods reported by the groups of Hopf, [10] de Meijere, [11] Longone, [12a] Misumi, [12b] and others have greatly actuated the formation of various molecular stacks such as ring-fused (2), bridge-extended (3), and quadruple stacks (4)a sw ell as other chemical topologies to examine molecular strain and transannular p-p interactions. [13] [2.2]Paracyclophane chemistry has evolved from functional molecules to functional materials and from synthetic curiosity to emerging applications in asymmetric synthesis,e nergy materials, p-stacked polymers,and functional parylene coatings (polymer made by polymerization of PCP induced by vapor-phase pyrolysis). [14] Numerous material applications dealing with planar chirality and through-space conjugation have been the subject of excellent reviews.…”

Section: Introduction and Historymentioning

confidence: 99%

Regioselective Functionalization of [2.2]Paracyclophanes: Recent Synthetic Progress and Perspectives

et al. 2019

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Abstract[2.2]Paracyclophane (PCP) is a prevalent scaffold that is widely utilized in asymmetric synthesis, π‐stacked polymers, energy materials, and functional parylene coatings that finds broad applications in bio‐ and materials science. In the last few years, [2.2]paracyclophane chemistry has progressed tremendously, enabling the fine‐tuning of its structural and functional properties. This Minireview highlights the most important recent synthetic developments in the selective functionalization of PCP that govern distinct features of planar chirality as well as chiroptical and optoelectronic properties. Special focus is given to the function‐inspired design of [2.2]paracyclophane‐based π‐stacked conjugated materials by transition‐metal‐catalyzed cross‐coupling reactions. Current synthetic challenges, limitations, as well as future research directions and new avenues for advancing cyclophane chemistry are also summarized.

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Section: Introduction and Historymentioning

confidence: 99%

Regioselective Functionalization of [2.2]Paracyclophanes: Recent Synthetic Progress and Perspectives

et al. 2019

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“…In the last couple of years, transition‐metal mediated cross‐coupling reactions have dramatically changed the face of modern paracyclophane chemistry . However, a common struggle in PCPs' synthetic transformation is the often unexpected and non‐analogue reactivity when compared to the seemingly similar benzene or p ‐xylene chemistry.…”

Section: Introductionmentioning

confidence: 99%

Preparation and Synthetic Applications of [2.2]Paracyclophane Trifluoroborates: An Efficient and Convenient Route to Nucleophilic [2.2]Paracyclophane Cross‐Coupling Building Blocks

et al. 2019

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We report the synthesis of [2.2]paracyclophane (PCP) trifluoroborate building blocks that can be used for the incorporation of the PCP moiety into a wide range of (hetero)aryl chlorides, bromides and triflates by a Pd(II)/RuPhos mediated Suzuki–Miyaura cross‐coupling reaction. The PCP trifluoroborate species are bench stable with extended shelf life and easily accessible on a multigram scale by a two‐step synthesis from commercially available PCP. They can be handled conveniently without special precautions, thus overcoming many of the limitations of other PCP cross‐coupling reagents. Additionally, a high yielding regioselective monolithiation/borylation protocol for the synthesis of pseudo‐para and pseudo‐ortho PCP halotrifluoroborates and their subsequent Suzuki–Miyaura cross‐coupling are described.

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“…In most cases, the norbornene (or norbornane) fragment does not appear in the final product. The characteristic common feature of all these transformations is that ortho-substituted aryl iodides (or bromides) undergo a second coupling in the other ortho position, hence the term norbornene shuttle was created by Lautens for this methodology, by which various selectively substituted bi-and teraryls (Figure 8.2) [362] as well as heterobi-, tri-, and higher oligocyclic systems can be obtained ( [370].…”

Section: Brmentioning

confidence: 99%

Cross‐Coupling of Organyl Halides with Alkenes – The Heck Reaction

Bräse¹,

Meijere²

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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The carbopalladation of an alkene by an organylpalladium halide is the essential step in one of the major contemporary metal-catalyzed C-C coupling reactions. About 45 years ago, a Japanese and an American group almost simultaneously designed and executed palladium-mediated coupling reactions of aryl and alkenyl halides with alkenes [1]. In subsequent investigations, Richard Heck and his group developed this reaction into a catalytic transformation and started to demonstrate its usefulness as well as its rather broad scope. The real push to utilize this powerful C-C-bondforming process, however, started only around the mid-1980s, and by now, an impressive number of publications have established the meanwhile so-called Heck reaction [2] 1) as an indispensable method in Organic Synthesis [3][4][5][6][7]. The universal recognition of the importance of the Heck reaction and the Negishi as well as the Suzuki coupling eventually won the Nobel Prize for Richard Heck along with Ei-ichi Negishi and Akira Suzuki in 2010. The applications of the Heck reaction range from the preparation of -functionalized and unfunctionalized -hydrocarbons, novel polymers, and dyes to new advanced enantioselective syntheses of natural products and biologically active nonnatural compounds. The more or less simultaneous developments of mechanistically related variants, namely, the Kumada, Suzuki, Stille, Hiyama, and Negishi coupling reactions (Chapters 12, 2, 3, 4, and 15, respectively) of metallated alkenes and arenes with aryl and alkenyl halides or the metal-catalyzed formation and cycloisomerization of enynes have drawn profit from the improvement of and mechanistic insights into the Heck reaction. This, of course, applies vice versa as well. Using only a catalytic amount of a palladium(0) complex or a precursor to a palladium species, the Heck reaction can bring about unprecedented structural changes, particularly when conducted intramolecularly. The full potential of this palladium-catalyzed process is still being further explored as demonstrated by a total of over 7000 publications in the past 40 years by 1) The alkynylation of aryl and alkenyl halides, frequently also considered as Heck reactions, is described in Chapter 6.

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New interesting molecular topologies by way of modern cross-coupling reactions

Cited by 28 publications

References 2 publications

Regioselective Functionalization of [2.2]Paracyclophanes: Recent Synthetic Progress and Perspectives

Regioselective Functionalization of [2.2]Paracyclophanes: Recent Synthetic Progress and Perspectives

Preparation and Synthetic Applications of [2.2]Paracyclophane Trifluoroborates: An Efficient and Convenient Route to Nucleophilic [2.2]Paracyclophane Cross‐Coupling Building Blocks

Cross‐Coupling of Organyl Halides with Alkenes – The Heck Reaction

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