Π-Face Diastereoselection: Stereochemistry and Reactivity of Addition Reactions on Conformationally Rigid Substrates: 5-X-Adamantan-2-ones and trans-10-X-Decal-2-ones

Stereochemistry and relative rates kax and keq of addition reactions on title compounds have been measured under eight different reaction conditions (MeMgI in Et2O and C6H6, MeMgCl in THF, MeLi at 20 and −78°C, Me2Zn in Et2O, Me3Al in the ratio 1:1 reactant:substrate in toluene and Me2CuLi/MeLi in Et2O at −78°C). Our kinetic data do not fit with current theories of π-face diastereoselection.