127321-10-2Relevant academic research and scientific papers
Nickel- and palladium-catalyzed cross-coupling reactions at the bridgehead of bicyclo[1.1.1]pentane derivatives - A convenient access to liquid crystalline compounds containing bicyclo[1.1.1]pentane moieties
Messner, Matthias,Kozhushkov, Sergei I.,De Meijere, Armin
, p. 1137 - 1155 (2007/10/03)
Radical addition reactions of organyl iodides 7a-s onto [1.1.1]propellane (2) followed by halogen-lithium exchange and transmetallation with zinc chloride, as well as additions of Grignard reagents to 2, have furnished a variety of 3-substituted bicyclo[1.1.1]pentyl-1-magnesium (14) and -zinc (19) derivatives. The latter have been coupled with various alkenyl, aryl, and biaryl halides and triflates under NiCl2dppe, Pd(PPh3)4, or PdCl2(dppf) catalysis to give a number of 1,3-disubstituted bicyclo[1.1.1]pentyl derivatives 17, 20, and 23, several of which exhibit liquid crystalline properties, in moderate to very good yields. The coupling products 20ca, 23ab, 23ae, 23ff, and 23fg have been further transformed to yield bicyclo[1.1.1]pentyl derivatives 32, 24ab, 24ae, 27ff, and 27fg, respectively, bearing alkynyl, cyano, and/or alkenyl groups.
Formation and reactions of bicyclo[1.1.1]pentyl-1 cations
Wiberg, Kenneth B.,McMurdie, Neil
, p. 11990 - 11998 (2007/10/03)
The ionization of 1-bicyclo[1.1.1]pentyl halides was shown to initially form the 1,3-bridged bicyclo[1.1.1]pentyl-l cation. It appears to be a transition state that leads to the bicyclo[1.1.0]butyl-1-carbinyl cation which can be trapped with azide ion and
Synthesis of Some Bridgehead-Bridgehead-Disubstituted Bicyclopentanes
Della, Ernest W.,Taylor, Dennis K.
, p. 2986 - 2996 (2007/10/02)
The synthesis of a wide variety of 1,3-disubstituted bicyclopentanes is described, with particular emphasis on the generation of a series of 3-X-substituted bicyclopentyl bromides required for solvolytic studies.Functional group manipulation at the bridgehead was readily accomplished in the majority of cases by radical processes; in some instances, transformations were effected via carbanionic-type intermediates.
Toward a molecular-size "Tinkertoy" construction set. Preparation of terminally functionalized [n]staffanes from [1.1.1]propellane
Kaszynski, Piotr,Friedli, Andrienne C.,Michl, Josef
, p. 601 - 620 (2007/10/02)
A facile but low-yield synthesis of [n]staffanes (the oligomers of [1.1.1.]propellane 1, n =1-5) functionalized on one or both ends is described, and their properties are summarized. The substituents are -COOCH3, -n-C4H9, -C6H5, -Br, -I, and -SCOCH3, and their conversion to others, such as -COOH, -COCH3 and -SH, is demonstrated. It is proposed that these rod-shaped molecules will be useful in the development of a molecular-size civil engineering construction set analogous to children's toy construction sets.
