Synthesis of Carbobicyclic Compounds via Palladium−Catalyzed Cyclization/Hydrosilylation:  Evidence for Reversible Silylpalladation

• Published in: Journal of organic chemistry Vol. 66; no. 5; pp. 1755 - 1760
• Main Authors: Wang, Xiang, Chakrapani, Harinath, Stengone, Carmine N., Widenhoefer, Ross A.
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 09.03.2001; Amer Chemical Soc
• Subjects: Bridged Bicyclo Compounds, Heterocyclic - chemical synthesis; Bridged Bicyclo Compounds, Heterocyclic - chemistry; Catalysis; Chemistry; Chemistry, Organic; Magnetic Resonance Spectroscopy; Molecular Structure; N-Acetylneuraminic Acid - chemistry; Palladium - chemistry; Physical Sciences; Science & Technology; Spectrophotometry, Infrared; METAL-PROMOTED CYCLIZATION; CYCLIC CARBOPALLADATION; COMPLEX; DIENES; ACYCLIC PRECURSORS; CONSTRUCTION; CASCADE CARBOALUMINATION; POLYENE CYCLIZATIONS; CARBOMETALATION; CARBOCYCLES
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo001438k

Cyclization/hydrosilylation of substituted 1-vinyl-1-(3-butenyl)cycloalkanes catalyzed by a 1:1 mixture of (phen)Pd(Me)Cl (1) and NaBAr4 [phen = 1,10-phenanthroline; Ar = 3,5-C6H3(CF3)2] formed silylated spirocycles in high yield with excellent regio and diastereoselectivity. Cyclization/hydrosilylation of substituted 3-(3-butenyl)cycloalkenes or 2,3-diallyl-5,6-dimethyl-1,4-hydroquinone diacetate (16) formed silylated fused bicyclic complexes in good yield. Reaction of substituted 1,6,11-nonatrienes with silane catalyzed by 1/NaBAr4 led to cascade cyclization with hydrosilylation. This latter procedure was employed in the synthesis of silylated bicyclopentanes and a linear triquinane.