Scope and facial selectivity of the Prins-pinacol synthesis of attached rings.
Using a B-alkyl Suzuki cross-coupling as a key step, a concise and stereocontrolled synthesis of five- to eight-membered triisopropylsiloxy ethers having (2Z)-(6,6-dimethoxyhexylidene) or (2Z)-(5,5-dimethoxypentylidene) side chains was developed. Prins-pinacol reactions of these precursors promoted by SnCl4 provide bicyclic products in which 5-, 6-, or 7-membered rings are joined by a C-C single bond. Synthetically challenging attached ring systems in which both rings are chiral can be prepared in this fashion with high stereo- and enantioselectivity. Stabilizing through-space electrostatic interactions between the alpha-alkoxycarbenium ion and an axially positioned oxygen substituent are believed to play a significant role in organizing the transition structure of the Prins cyclization.
Overman
Larry E
LE
Department of Chemistry, 516 Rowland Hall, University of California, Irvine, California 92697-2025, USA. leoverma@uci.edu
Velthuisen
Emile J
EJ
D003432:Cross-Linking Reagents / Q000737:chemistry; D003500:Cyclization; D004987:Ethers / Q000737:chemistry; D006574:Heterocyclic Compounds, 2-Ring / Q000138:chemical synthesis*; D055672:Static Electricity; D013237:Stereoisomerism
D003432:Cross-Linking Reagents; D004987:Ethers; D006574:Heterocyclic Compounds, 2-Ring