32405-37-1

Upstream product

• 930-99-4 (3aS,6aS)-1,2,3,3a,4,6a-Hexahydro-pentalene 
• 79643-80-4 (+/-)-trimethyl(9-oxabicyclo[6.1.0]non-1-yl)silane 

Downstream Products

• 82131-54-2 tricyclo[5.3.1.0^4,11]undecan-8-ol tosylate 
• 43000-53-9 tricyclo[5.2.1.0^3,8]undecane 
• 1551-76-4 endo-2-methyl-cis-bicyclo<3.3.0>octane 
• 82131-56-4 Toluene-4-sulfonic acid (2aR,4aS,6aR,6bR)-1-(decahydro-cyclopenta[cd]pentalen-1-yl)methyl ester 
• 82131-57-5 Toluene-4-sulfonic acid (1S,2aR,4aS,6aR,6bR)-(decahydro-cyclopenta[cd]pentalen-1-yl) ester 
• 72028-18-3 cis-bicyclo[3.3.0]oct-endo-2-ylcarbonyl chloride 
• 7403-22-7 (+/-)-(3ar,6ac)-octahydro-pentalene-1t-carboxylic acid 
• 57595-39-8 tetrahydrotriquinacene 
• 74532-61-9 (2S,3aS,6aS)-2-Benzenesulfonyl-2-(2-trimethylsilanylmethyl-allyl)-hexahydro-pentalen-1-one 
• 74532-67-5 (3aR,3bR,6aR,7aR)-7a-Benzenesulfonyl-2-methylene-decahydro-cyclopenta[a]pentalen-3a-ol 
• 74532-81-3 (3aR,6aR)-2-Benzenesulfonyl-hexahydro-pentalen-1-one 

Relevant academic research and scientific papers

Palladium(0)-catalyzed cyclization-carbonylation of 2,7-octadienyl acetate and homologues

The palladium(0)-catalyzed carbonylations, in acetic acid as a necessary solvent, of 2,7-octadienyl acetate and homologues via π-allylpalladium species were preceded by their intramolecular olefin insertion to form mixtures of cis/trans-2-vinylcyclopentylacetyl- and cis/trans-cyclohexylacetylpalladium intermediates, which undergo further the intramolecular (5-exo) Heck reaction to give bicyclo-[3.3.0] and [4.3.0] skeletons, respectively, except for one case affording trans-2-vinylcyclopentylacetic acid as a major product.

Structural Effects in Solvolytic Reactions. 50. Steric Retardation in the Solvolysis of Tertiary Endo Bicyclic Derivatives. Evidence That the Exo:Endo Rate/Product Ratios for typical Reactions in Rigid U-Shaped Bicyclics Is a General Steric Phenomenon

The exo:endo rate ratios for the solvolysis in 80percent acetone at 25 deg C of the p-nitrobenzoates of tertiary bicyclic alcohols of widely varying U-shape character, such as 2-methyl- and 3-methyl-cis-bicyclooctanols, 2-methyl-2-norbornanol, and 2-, 8-, and 9-methyl-endo-5,6-trimethylene-2-, -8-, and -9-norbornanols increase with increasing U-shape character of the bicyclic skeleton.This supports the proposal that steric retardation of ionization of the endo isomer is a major factor in governing the exo:endo rate ratios in these tertiary systems.A comparison of the solvolysis data with those of representative nonsolvolytic reactions in these U-shaped systems indicates that the exo/endo relative reactivities reveal a similar pattern for all of the reactions.The exo:endo ratios (product or rate) increase with increasing U-shape character of the bicyclic skeleton.Thus the large exo:endo rate ratio in the solvolysis of tertiary 2-norbornyl derivatives may as well be due to steric rather than to the long proposed electronic factor.

CYCLIC α,β-EPOXYSILANES ACID-CATALYSED REACTIONS OF 1-TRIMETHYLSILYLCYCLOOCTENE OXIDE

The acid-catalysed reactions of medium ring α,β-epoxysilane 1 are described.The epoxide 1 gives exclusively the bicyclic alcohol 2 with boron trifluoride etherate.With aqueous sulphuric acid the products are due to both transannular ring closure, 2, and transannular hydride migration, 3 and 4. trans-Cyclooctene derivatives 3 and 4 are formed by the trans-elimination of trimethylsilanol from the likely intermediate β-hydroxysilanes 10 and 11.The results with methanolic sulphuric acid are similar.It is also noticed that the hydride migration is facilitated by the nucleophilic strength of the medium.