1. Oxymercuration kinetically controlled; high energy TS’s ≠ kinetically controlled; low energy TS’s ≠ 1 2 Total of 8 racemates possible. Only 2 are formed. 12

2. Oxymercuration – II; Add a Methyl Group regiochemistry; anti addition; anti - Markovnikov regiochemistry; anti addition; Markovnikov boatlike TS ≠ eliminated on previous slide wrong regiochemistry Only product!!! 1 2

3. Oxymercuration - III If BD 4 - had been used as the reductant, a mixture of deuterio compounds would form.

4. Oxymercuration - IV anti addition; Markovnikov diastereomers anti addition; Markovnikov diastereomers radical intermediate

5. Alkyl Mercurials – Radical Oxygenation RHgBr + BH 4 - --------> RHgH RHgH ---------> R. +. HgH R. + O 2 ---------> ROO. ROO. +. HgH -------> ROOH + Hg 0 ROOH + BH 4 - --------> ROH Endo and exo mercurials give the same radical. Product distributions the same. = R endo exo C. L. Hill and G. M. Whitesides, J. Am. Chem. Soc., 96, 1974, 870.