105542-98-1Relevant articles and documents
Scalable synthesis of 1-bicyclo[1.1.1]pentylamine via a hydrohydrazination reaction
Bunker, Kevin D.,Sach, Neal W.,Huang, Qinhua,Richardson, Paul F.
, p. 4746 - 4748 (2011)
The reaction of [1.1.1]propellane with di-tert-butyl azodicarboxylate and phenylsilane in the presence of Mn(dpm)3 to give di-tert-butyl 1-(bicyclo[1.1.1]pentan-1-yl)hydrazine-1,2-dicarboxylate is described. Subsequent deprotection gives 1-bicyclo[1.1.1]pentylhydrazine followed by reduction to give 1-bicyclo[1.1.1]pentylamine. The reported route marks a significant improvement over the previous syntheses of 1-bicyclo[1.1.1] pentylamine in terms of scalability, yield, safety, and cost.
Cubane, Bicyclo[1.1.1]pentane and Bicyclo[2.2.2]octane: Impact and Thermal Sensitiveness of Carboxyl-, Hydroxymethyl- and Iodo-substituents
Dallaston, Madeleine A.,Houston, Sevan D.,Williams, Craig M.
, p. 11966 - 11970 (2020)
With the burgeoning interest in cage motifs for bioactive molecule discovery, and the recent disclosure of 1,4-cubane-dicarboxylic acid impact sensitivity, more research into the safety profiles of cage scaffolds is required. Therefore, the impact sensitivity and thermal decomposition behavior of judiciously selected starting materials and synthetic intermediates of cubane, bicyclo[1.1.1]pentane (BCP), and bicyclo[2.2.2]octane (BCO) were evaluated via hammer test and sealed cell differential scanning calorimetry, respectively. Iodo-substituted systems were found to be more impact sensitive, whereas hydroxymethyl substitution led to more rapid thermodecomposition. Cubane was more likely to be impact sensitive with these substituents, followed by BCP, whereas all BCOs were unresponsive. The majority of derivatives were placed substantially above Yoshida thresholds—a computational indicator of sensitivity.
ADDITION OF HALOGENS TO PROPELLANE
Zefirov, N. S.,Surmina, L. S.,Sadovaya, N. K.,Koz'min, A. S.
, p. 2670 (1987)
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Synthesis of novel cage quaternary salts via nucleophilic substitution of 1,3-diiodobicyclo[1.1.1 ]pentane. Further evidence for a stable 3-iodo-1-bicyclo[1.1.1]pentyl cation
Adcock, James L.,Gakh, Andrei A.
, p. 4875 - 4878 (1992)
Nucleophilic substitution of 1,3-diiodobicyclo[1.1.1]pentane by tertiary amines and pyridines was investigated. The structure of cage quaternary salts obtained together with the observation of the competitive addition of pyridine in the reaction of [1.1.1]propellane with iodine indicate the existence of a relatively stable "hot intermediate" very close in its structure to a stabilized 3-iodo-1-bicyclo[1.1.1]pentyl cation.
Visible-Light-Induced 1,3-Aminopyridylation of [1.1.1]Propellane with N-Aminopyridinium Salts
Shin, Sanghoon,Lee, Seojin,Choi, Wonjun,Kim, Namhoon,Hong, Sungwoo
supporting information, p. 7873 - 7879 (2021/03/08)
Through the formation of an electron donor–acceptor (EDA) complex, strain-release aminopyridylation of [1.1.1]propellane with N-aminopyridinium salts as bifunctional reagents enabled the direct installation of amino and pyridyl groups onto bicyclo[1.1.1]pentane (BCP) frameworks in the absence of an external photocatalyst. The robustness of this method to synthesize 1,3-aminopyridylated BCPs under mild and metal-free conditions is highlighted by the late-stage modification of structurally complex biorelevant molecules. Moreover, the strategy was extended to P-centered and CF3 radicals for the unprecedented incorporation of such functional groups with pyridine across the BCP core in a three-component coupling. This practical method lays the foundation for the straightforward construction of new valuable C4-pyridine-functionalized BCP chemical entities, thus significantly expanding the range of accessibility of BCP-type bioisosteres for applications in drug discovery.
Divergent Strain-Release Amino-Functionalization of [1.1.1]Propellane with Electrophilic Nitrogen-Radicals
Kim, Ji Hye,Ruffoni, Alessandro,Al-Faiyz, Yasair S. S.,Sheikh, Nadeem S.,Leonori, Daniele
supporting information, p. 8225 - 8231 (2020/03/04)
Herein we report the development of a photocatalytic strategy for the divergent preparation of functionalized bicyclo[1.1.1]pentylamines. This approach exploits, for the first time, the ability of nitrogen-radicals to undergo strain-release reaction with [1.1.1]propellane. This reactivity is facilitated by the electrophilic nature of these open-shell intermediates and the presence of strong polar effects in the transition-state for C?N bond formation/ring-opening. With the aid of a simple reductive quenching photoredox cycle, we have successfully harnessed this novel radical strain-release amination as part of a multicomponent cascade compatible with several external trapping agents. Overall, this radical strategy enables the rapid construction of novel amino-functionalized building blocks with potential application in medicinal chemistry programs as p-substituted aniline bioisosteres.