Synthesis and applications of highly functionalized 1-halo-3-substituted bicyclo[1.1.1]pentanes

Abstract

A wide range of halogenated bicyclo[1.1.1]pentanes are accessed by functional group tolerant radical ring-opening of tricyclo[1.1.1.01,3]pentane, using triethylborane as initiator.

Nonconjugated Hydrocarbons as Rigid‐Linear Motifs: Isosteres for Material Sciences and Bioorganic and Medicinal Chemistry

“…Recent work has also shown the applicability of alkyl iodide substitution with 6 to form iodoalkyl BCP products 114 . These compounds are achieved under mild conditions using 10 mol % of the Lewis acid triethylborane at room temperature and the reaction is often completed within 15 min.…”

“…Recent work has also shownt he applicability of alkyl iodide substitution with 6 to form iodoalkyl BCP products 114. [180] These compounds are achievedu nder mild conditions using 10 mol %o ft he Lewis acid triethylborane at room temperature and the reactioni so ften completed within 15 min. Importantly,i nt he absence of triethylborane, no product formation was observedi nt he dark or light, highlighting its necessity.A lso noteworthy was the absence of any staffane byproducts from the reaction.…”

Selected Topics in the Syntheses of Bicyclo[1.1.1]Pentane (BCP) Analogues

“…[1.1.1]Propellane ( 2 ) was converted to 3‐alkylbicyclo[1.1.1]pentan‐1‐yl iodide ( 36 b – h ), which was converted to the corresponding carboxylic acids ( 38 a – g ) in 42–91% overall yields . Recently, Anderson and co‐workers further established the synthetic utility of such transformation by optimizing the carboiodination of [1.1.1]propellane ( 2 ) via radical mechanisms induced by triethylborane–oxygen or electrochemistry processes …”

Bicyclo[1.1.1]pentyl Sulfoximines: Synthesis and Functionalizations

“…The recent focus on saturated hydrocarbons as structural motifs ('escape from flatland') [1] has drawn the attention of many groups towards bicyclo[1.1.1]pentanes (BCPs). [2] Derived from [1.1.1]propellane (4), there have been numerous contributions to the synthesis of BCPs with CÀ C, [3] CÀ N [4] and CÀ S [5] bond formations. The modification of these products is an emerging field [6] and besides oxidation [5a,7] BCP sulfides 5 have not been addressed so far.…”

“…Sulfoximine-containing drug candidates by Bayer (1), Amgen (2) and Boehringer Ingelheim(3). Preliminary work by our group in the synthesis of BCP-sulfides 5 and 6, summary of sulfoximine precursors, Narylations of sulfoximines and content of this work.…”