Stereochemical aspects of proton chemical shifts. VII. The γ effects of hydroxyl,methoxyl and methyl substituents

The ¹H NMR chemical shifts of some hydroxy, methoxy or methyl substituted trans-decalins, trans-1, 3-dioxadecalins and cyclohexanes are reported. It is concluded that the replacement in a g⁺g⁺ H? C? C? C? H fragment of one hydrogen by hydroxy, methoxy or methyl results in a modest (0.1 ppm) upfield shift of the other hydrogen atom. Experimental limitations to the transferability of shift increments from one molecular environment to another are demonstrated. The syntheses of 1α,5β-dimethoxy- and 1β,5α-dimethoxy-trans-decalin are given.