Isolation of isobenzofuran, a stable but highly reactive molecule

Warrener, Ronald N.

doi:10.1021/ja00738a057

Cited by 151 publications

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“…7-Oxanorbornadienes 22 can only be used as A-BLOCK partners in this reaction as any attempt to create a B-BLOCK from reaction of 22 with 3,6-di(2-pyridyl)-s-tetrazine results in rapid fragmentation of the dihydropyridazine to the corresponding isobenzofuran. 25 A significant advance in the production of mixed metal complexes of ditopic ligands came with the finding that metal complexes of phenanthroline-containing A or B-BLOCKs could be coupled using ACE technology. Thus, the ruthenium (II) complex 24 of the cyclobutene epoxide B-BLOCK 19 was heated with the osmium (II) complex 25 formed from A-BLOCK phenanthroline 16 to yield heterodinuclear complex 26, a coupled product containing both types of metal complex (Scheme 7).…”

Section: Figurementioning

confidence: 99%

Fundamental Principles of BLOCK Design and Assembly in the Production of Large, Rigid Molecules with Functional Units (Effectors) Precisely Located on a Carbocyclic Framework

Warrener¹,

Butler²,

Russell³

1998

Synlett

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IntroductionThere have been immense changes in chemistry and related sciences in the last decade, a period which has seen the emergence of supramolecular chemistry, a quantum jump in the sophistication of host-guest chemistry and the advent of molecular modelling and computational techniques for the working chemist. Combined with this, has been the breaking down of traditional subject barriers, the growth of new ones and a more interdisciplinary approach to science, especially at the research level. The increased range and sophistication of instrumentation, especially NMR has also made its mark.A key player in this new era of science at the molecular level has been the Molecular Architect (Engineer). This person needs to appreciate function in molecular terms, as well as being able to work at the supramolecular level and to be involved in design at the most advanced molecular levels. Self assembly, self replicating systems and nanotechnology are some of the emerging areas where this can be expressed and certainly fall within the bailiwick of the Molecular Architect.Our interest in rigid 3D organic structures had facets of several of the above mentioned topics, but we approached the synthesis of such systems as builders of molecules. We drew on a strong background in organic synthesis and took on board the tenets of good design, including the concepts of retrosynthesis and convergency of approach. In addition, the methods of natural synthesis and the part that enzymes play in protein and nucleic acid synthesis were factored in as instructive role models.The emergence of robotic procedures in chemistry and the upsurge of combinatorial methodology have also impacted on our quest for a new modular approach to supramolecular systems. We appreciated that we required strongly focussed goals and selected systems based on fused rings (alicyclic, aromatic or heterocyclic) with a strong bias towards fused alicyclic systems as our rigid molecular framework (molracs 5 ).The building blocks of our youth such as LEGO ® , Meccano ® and Tinkertoys ® to name a few, had left their mark for modular assembly and this was indeed, a good starting point. We envisaged collecting a kit of small molecules which could be assembled into large rigid molecular systems using stereospecific bond-forming (linking) techniques. The elements of shape and functionality would be addressed in the assembly process which should be simple and able to be achieved by non-specialist organic chemists. The longer term goal was to provide an automated procedure where individual BLOCKs could be called up by computer and assembled as required by the client. This final point highlights a service and advisory role for the Molecular Architect, where strong client interface is paramount.Within this background, the BLOCK concept 6 had its foundation and we set up a program to develop:• the design and synthesis of building BLOCKs • assembly procedures• protocols for attaching the effectors.Abstract: New cycloaddition reactions have been developed to regiospecifically c...

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Section: Figurementioning

confidence: 99%

Fundamental Principles of BLOCK Design and Assembly in the Production of Large, Rigid Molecules with Functional Units (Effectors) Precisely Located on a Carbocyclic Framework

Warrener¹,

Butler²,

Russell³

1998

Synlett

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“…This reaction was exploited in a bioorthogonal context to detect RNA . Isoindoles and isobenzofurans are high‐energy molecules, and we hypothesized that leaving groups connected via a methylene to the heterocyclic ring would spontaneously dissociate. We designed benzonorbornadienes with carbamate leaving groups attached via a methylene linker to the bridgehead position (Scheme ) .…”

Section: Reported Dissociative Bioorthogonal Reactionsmentioning

confidence: 99%

“…In this design, a tetrazine quenches a nearby fluorophore, and reaction with the benzonorbornadiene converts it into the pyridazine, which does not quench the dye, thus turning on the fluorescence signal . Because the formed adduct undergoes a cycloreversion, the strands are not ligated; dissociation of the reacted oligonucleotide probes from the template enables rapid signal amplification by probe turn‐over. The same group developed probes based on vinyl ether groups reacting with tetrazines .…”

Section: Applications Of Dissociative Bioorthogonal Reactions In the mentioning

confidence: 99%

Dissociative Bioorthogonal Reactions

Franzini

2019

ChemBioChem

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Bioorthogonal reactions that proceed readily under physiological conditions without interference from biomolecules have found widespread application in the life sciences. Complementary to the bioorthogonal reactions that ligate two molecules, reactions that release a molecule or cleave a linker are increasingly attracting interest. Such dissociative bioorthogonal reactions have a broad spectrum of uses, for example, in controlling bio‐macromolecule activity, in drug delivery, and in diagnostic assays. This review article summarizes the developed bioorthogonal reactions linked to a release step, outlines representative areas of the applications of such reactions, and discusses aspects that require further improvement.

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“…Availability of 48 opened the route to isocorannulenofuran 44 by the well-established "s-tetrazine approach", [45] which involved a brief heating of 48 with commercially available 2,6-bis-2-pyridyl-1,2,4,5-tetrazine in chloroform, followed by filtration of the purple reaction mixture through a plug of silica gel. This procedure provided isocorannulenofuran 44 in 94 % yield (Scheme 12, top).…”

Section: Corannulene-based Synthons: Corannulyne and Isocorannulenofuranmentioning

confidence: 99%

Chemistry on a Half‐Shell: Synthesis and Derivatization of Buckybowls

2011

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Buckybowls, bowl‐shaped polycyclic aromatic hydrocarbons structurally related to fullerenes, represent a class of hydrocarbons with unique properties and a potential for application as novel materials. This review outlines the development of the practical preparations of buckybowls, starting with the original synthesis of corannulene achieved in 1966. A particular attention is paid to the last decade developments which include construction of large, highly nonplanar molecular networks (molecular clips and tweezers) capable of binding guest molecules of various sizes and shapes. In particular, such molecular clips were proven to form stable supramolecular complexes with fullerenes C60 and C70, both in solution and in the solid state.

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Isolation of isobenzofuran, a stable but highly reactive molecule

Abstract: for the mass spectra (recorded on an AEI MS902 instrument, operated at 70 eV).(19) E. Le Goff and R. B. LaCount, Tetrahedron Lett., 2787 (1965).(20) G. M. Badger, "Aromatic Character and Aromaticity," Cambridge University Press, Cambridge, 1969, p 61. (21) We thank Dr.

Cited by 151 publications

References 0 publications

Fundamental Principles of BLOCK Design and Assembly in the Production of Large, Rigid Molecules with Functional Units (Effectors) Precisely Located on a Carbocyclic Framework

Fundamental Principles of BLOCK Design and Assembly in the Production of Large, Rigid Molecules with Functional Units (Effectors) Precisely Located on a Carbocyclic Framework

Dissociative Bioorthogonal Reactions

Chemistry on a Half‐Shell: Synthesis and Derivatization of Buckybowls

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