Organotransition metal [3+2] cycloaddition reactions

Frühauf, Hans‐Werner

doi:10.1016/s0010-8545(01)00465-9

Cited by 49 publications

(32 citation statements)

References 92 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Materials and Methods: 1,3-Dimesitylimidazolylidene (1) [35] and aryl azides (2) [50,51] were prepared as described previously. Solvents were dried and degassed by a Vacuum Atmospheres Company solvent purification system (model 103991) and stored over 3 Å molecular sieves in a nitrogen-filled glove box.…”

Section: Methodsmentioning

confidence: 99%

“…Modern chemistry has benefited from the synthetic power and versatility of dipolar cycloaddition and cyclization reactions, [1][2][3][4] which have enabled far-reaching advances in many pursuits, from the preparation of unnatural β-amino acids, [5] to the kinetic resolution of stereoisomers, [6] to the functionalization of carbon nanotubes. [7] Alkyne-azide 1,3-dipolar cycloadditions are an especially practical subclass of reactions, given that molecules comprising terminal alkyne [8][9][10] and azide [11] functionalities are synthetically accessible and often commercially available.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Methylation of Ylidene‐Triazenes: Insight and Guidance for 1,3‐Dipolar Cycloaddition Reactions

et al. 2010

View full text Add to dashboard Cite

Reaction of 1,3-dimesitylimidazolylidene (1) with p-functionalized phenyl azides 2 (a: H, b: OCH 3 , c: NO 2 ) afforded the respective imidazolylidene-triazenes 3 in good yields (65-99 %). Subsequent treatment with methyl iodide produced the corresponding methylated products 4 in near-quantitative yields (99 %). Analysis by NOESY 1D NMR spectroscopy and single-crystal X-ray diffraction revealed that the methylation reaction was regioselective and occurred at the nitrogen atom most distal from the heterocycle. Consistent with the formation of ionic salts, the 1 H NMR signals for the imidazole protons in 4 were shifted Ͼ 0.5 ppm downfield compared to 1, indicating the accumulation of positive charge.

show abstract

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Methylation of Ylidene‐Triazenes: Insight and Guidance for 1,3‐Dipolar Cycloaddition Reactions

et al. 2010

View full text Add to dashboard Cite

show abstract

“…2). 202 Although of this latter process also forms the basis of the catalytic, osmium(VIII)-mediated dihydroxylation and aminohydroxylation of alkenes and thus firmly established in the canon of organic synthesis, 203 the preparation of diamines through this approach has proven to be considerably more challenging.…”

Section: Transition Metal-catalyzed Diaminationmentioning

confidence: 99%

Methods for direct alkene diamination, new & old

2012

View full text Add to dashboard Cite

The 1,2-diamine moiety is a ubiquitous structural motif present in a wealth of natural products, including non-proteinogenic amino acids and numerous alkaloids, as well as in pharmaceutical agents, chiral ligands and organic reagents. The biological activity associated with many of these systems and their chemical utility in general has ensured that the development of methods for their preparation is of critical importance. While a wide range of strategies for the preparation of 1,2-diamines have been established, the diamination of alkenes offers a particularly direct and efficient means of accessing these systems. The purpose of this review is to provide an overview of all methods of direct alkene diamination, metal-mediated or otherwise.

show abstract

“…Remarkably, cycloadditions to metal–carbonyl bonds occur with maintenance of the metal–carbon (M–C) bond. 8,9 Hawthorne and co-workers reported the reaction between m -fluorobenzonitrile N -oxide and rhodacarborane anion [Rh-(PPh 3 )(CO)(C 2 B 9 H 11 )] − as the first 1,3-dipolar addition to a metal–carbon bond (Figure 1). 10 …”

Section: Introductionmentioning

confidence: 99%

1,3-Dipolar Cycloaddition Reactions of Low-Valent Rhodium and Iridium Complexes with Arylnitrile N-Oxides

et al. 2017

View full text Add to dashboard Cite

The reactions between low-valent Rh(I) and Ir(I) metal–carbonyl complexes and arylnitrile oxides possess the electronic and structural features of 1,3-dipolar cycloadditions. Density functional theory (DFT) calculations on these reactions, involving both cyclopentadienyl and carboranyl ligands on the metal carbonyl, explain the ease of the chemical processes and the stabilities of the resulting metallaisoxazolin-5-ones. The metal–carbonyl bond has partial double bond character according to the Wiberg index calculated through NBO analysis, and so the reaction can be considered a normal 1,3-dipolar cycloaddition involving M═C bonds. The rates of formation of the metallacycloadducts are controlled by distortion energy, analogous to their organic counterparts. The superior ability of anionic Ir complexes to share their electron density and accommodate higher oxidation states explains their calculated higher reactivity toward cycloaddition, as compared to Rh analogues.

show abstract

Organotransition metal [3+2] cycloaddition reactions

Cited by 49 publications

References 92 publications

Methylation of Ylidene‐Triazenes: Insight and Guidance for 1,3‐Dipolar Cycloaddition Reactions

Methylation of Ylidene‐Triazenes: Insight and Guidance for 1,3‐Dipolar Cycloaddition Reactions

Methods for direct alkene diamination, new & old

1,3-Dipolar Cycloaddition Reactions of Low-Valent Rhodium and Iridium Complexes with Arylnitrile N-Oxides

Contact Info

Product

Resources

About