83249-23-4Relevant academic research and scientific papers
1,3-Difunctionalizations of [1.1.1]Propellane via 1,2-Metallate Rearrangements of Boronate Complexes
Aggarwal, Varinder K.,Jing, Changcheng,Noble, Adam,Yu, Songjie
, p. 3917 - 3921 (2020)
1,3-Disubstituted bicyclo[1.1.1]pentanes (BCPs) are valuable bioisosteres of para-substituted aromatic rings. The most direct route to these structures is via multicomponent ring-opening reactions of [1.1.1]propellane. However, challenges associated with these transformations mean that difunctionalized BCPs are more commonly prepared by multistep reaction sequences with BCP-halide intermediates. Herein, we report three- and four-component 1,3-difunctionalizations of [1.1.1]propellane with organometallic reagents, organoboronic esters, and a variety of electrophiles. This process is achieved by trapping intermediate BCP-metal species with boronic esters to form boronate complexes, which are versatile intermediates whose electrophile-induced 1,2-metallate rearrangement chemistry enables a broad range of C?C bond-forming reactions.
Polar Substituent Effects in 1,3-Disubstituted Bicyclopentanes
Applequist, Douglas E.,Renken, Terry L.,Wheeler, James W.
, p. 4985 - 4995 (2007/10/02)
The pKa's of eight 3-substituted bicyclopentanecarboxylic acids have been measured and found to correlate well with ?I constants.The value of ρI (2.23 +/- 0.12) is large but not large enough to propose any special perturbation of normal field-inductive effects by the close proximity (about 1.88 Ae) of the bridgehead carbons.Also determined were the products and rates of solvolyses of the p-nitrobenzoates of three 3-substituted 1-pentanes.The products were primarily unrearranged, and the rates again showed no surprisingsubstituent effects.A practical synthesis of 1,3-disubstituted bicyclopentanes has been developed and is described.
