Synthesis and reactions of two stereoisomeric [4.5.5.5]fenestranes with bridgehead substituents

• Published in: Tetrahedron Vol. 67; no. 21; pp. 3874 - 3880
• Main Authors: Weyermann, Philipp, Keese, Reinhart
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 27.05.2011; Elsevier
• Subjects: Alicyclic compounds; Alicyclic compounds, terpenoids, prostaglandins, steroids; Chemistry; Chemistry, Organic; Elimination reactions; Exact sciences and technology; Fenestranes; General and physical chemistry; Olefin–enone photocylcoaddition; Organic chemistry; Pauson–Khand-cyclocarbonylation; Photochemistry; Physical chemistry of induced reactions (with radiations, particles and ultrasonics); Physical Sciences; Planarizing distortions; Preparations and properties; Science & Technology; Pauson–Khand-cyclocarbonylation; Olefin–enone photocylcoaddition; Elimination reactions; Fenestranes; Planarizing distortions; Pauson-Khand-cyclocarbonylation; Olefin-enone photocylcoaddition; ESTERS; Stereoisomer; Cyclocarbonylation; Pauson—Khand—cyclocarbonylation; Ketol; Distortion; Photochemical reaction; Dehydration; Ring cleavage; Cycloaddition; Olefin; Pauson Khand reaction; Chemical synthesis; Enone; Ethylenic compound
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2011.03.086

The [4.5.5.5]fenestranes 2 and 3 with two different functionalities were prepared in seven steps with overall yields of 5% and 10%, respectively. For introduction of a bridgehead double bond the removal of the tertiary hydroxy group was investigated in the two stereoisomeric hydroxyketones 12 and 15. Whereas the dehydration readily occurred in 12, a ring opening reaction was observed for 15. [Display omitted]