99058-02-3Relevant articles and documents
Intermolecular Allene Functionalization by Silver-Nitrene Catalysis
Rodríguez, Manuel R.,Besora, María,Molina, Francisco,Maseras, Feliu,Díaz-Requejo, M. Mar,Pérez, Pedro J.
supporting information, p. 13062 - 13071 (2020/09/01)
Under silver catalysis conditions, using [Tp*,BrAg]2 as the catalyst precursor, allenes react with PhI═NTs in the first example of efficient metal-mediated intermolecular nitrene transfer to such substrates. The nature of the substituent at the allene seems crucial for the reaction outcome since arylallenes are converted into azetidine derivatives, whereas methylene aziridines are the products resulting from alkylallenes. Mechanistic studies allow proposing that azetidines are formed through unstable cyclopropylimine intermediates, which further incorporate a second nitrene group, both processes being silver-mediated. Methylene aziridines from alkylallenes derive from catalytic nitrene addition to the allene double bonds. Both routes have resulted to be productive for further synthetic transformations affording aminocyclopropanes.
Stereoselective Desymmetrization of gem-Diborylalkanes by “Trifluorination”
Kumar, Nivesh,Reddy, Reddy Rajasekhar,Masarwa, Ahmad
supporting information, p. 8008 - 8012 (2019/05/28)
An efficient and general method for the chemoselective synthesis of unsymmetrical gem-diborylalkanes is reported. This method is based on a late-stage desymmetrization through nucleophilic “trifluorination”, providing chiral gem-diborylalkanes bearing a trifluoroborate group. The reaction offers a highly modular and diastereoselective approach towards the synthesis of gem-diborylcyclopropanes. The utility of the gem-diborylalkane building blocks was demonstrated by selective post-functionalization of the trifluoroborate group. These functionalizations include inter- and intra- Pd-catalyzed Suzuki–Miyaura coupling reactions.
Can relief of ring-strain in a cyclopropylmethyllithium drive the Brook rearrangement?
Clayden, Jonathan,Watson, David W.,Chambers, Mark
, p. 3195 - 3203 (2007/10/03)
α-Cyclopropyl-α-trialkylsilyl alkoxides were formed either by addition of cyclopropyllithiums to acylsilanes or by addition of organolithiums to a cyclopropylformylsilane. [1,2]-Brook rearrangement led to α-silyloxy organolithiums which on warming underwent cyclopropane ring opening and [1,5]-retro-Brook rearrangement to yield γ-silyl ketones. Despite the favourability of the cyclopropane ring opening, the Brook rearrangement still required the presence of an anion stabilising group to proceed. β-Silylketones were similarly formed by Brook-retro-Brook rearrangement on warming acylsilanes with a vinyllithium.