Bicyclo[3.2.1]octane Synthons from Cyclopropenes:  Functionalization of Cycloadducts by Nucleophilic Additions

• Published in: Journal of organic chemistry Vol. 69; no. 2; pp. 406 - 416
• Main Authors: Orugunty, Ravi S, Wright, Dennis L, Battiste, Merle A, Helmich, Richard J, Abboud, Khalil
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 23.01.2004; Amer Chemical Soc
• Subjects: Alicyclic compounds; Alicyclic compounds, terpenoids, prostaglandins, steroids; Chemistry; Chemistry, Organic; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives; Organic chemistry; Physical Sciences; Preparations and properties; Science & Technology; KETONES; CYCLOADDITION REACTIONS; DIELS-ALDER REACTIONS; REDUCTION; STEREOSELECTIVITY; CONJUGATED DIENES; SUBSTITUENTS; OXYALLYL CATIONS; GRIGNARD-REAGENTS; Cycloaddition; Functionalization; Furan derivatives; Bicyclic compound; Selectivity; Chemical synthesis; Organic halogen compounds; Nucleophilic addition
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo035240m

It has been known for several decades that a highly functionalized family of tetrahalobicyclo[3.2.1]octadienes are readily available through the cycloaddition of furan or cyclopentadiene with either tetrachloro- or tetrabromocyclopropene. However, the application of these highly functionalized building blocks in synthesis has remained relatively unexplored in relation to their better-known counterparts derived through oxyallyl cation additions. As a first step toward utilizing these highly versatile intermediates in synthesis, a study of the addition of various nucleophiles to the halogenated nucleus has been conducted. It has been found that these halogenated systems are amenable to a wide range of functionalizations in high yields and with good selectivities.