Hah! I always seem to forget about those unique Wolfram Language functions that would make my life easier...iterating over strings is only intuitive and easy for me because it's a pretty standard technique across languages (probably for performance purposes).
Below is a small performance comparison between methods on my machine. The one using RealDigits is slightly faster (also gave me one extra digit for a full 200 i.e. has better precision); gotta work harder at changing my perspective!
ToExpression[Drop[StringSplit[ToString[N[E, 200]], ""], 2]] // Timing
(*{0.000937, {7, 1, 8, 2, 8, 1, 8, 2, 8, 4, 5, 9, 0, 4, 5, 2, 3, 5, 3, 6, 0, 2, 8, 7, 4, 7, 1, 3, 5, 2, 6, 6, 2, 4, 9, 7, 7, 5, 7, 2, 4, 7, 0, 9, 3, 6, 9, 9, 9, 5, 9, 5, 7, 4, 9, 6, 6, 9, 6, 7, 6, 2, 7, 7, 2, 4, 0, 7, 6, 6, 3, 0, 3, 5, 3, 5, 4, 7, 5, 9, 4, 5, 7, 1, 3, 8, 2, 1, 7, 8, 5, 2, 5, 1, 6, 6, 4, 2, 7, 4, 2, 7, 4, 6, 6, 3, 9, 1, 9, 3, 2, 0, 0, 3, 0, 5, 9, 9, 2, 1, 8, 1, 7, 4, 1, 3, 5, 9, 6, 6, 2, 9, 0, 4, 3, 5, 7, 2, 9, 0, 0, 3, 3, 4, 2, 9, 5, 2, 6, 0, 5, 9, 5, 6, 3, 0, 7, 3, 8, 1, 3, 2, 3, 2, 8, 6, 2, 7, 9, 4, 3, 4, 9, 0, 7, 6, 3, 2, 3, 3, 8, 2, 9, 8, 8, 0, 7, 5, 3, 1, 9, 5, 2, 5, 1, 0, 1, 9, 0}}*)
Rest[Flatten[RealDigits[E, 10, 200]]] // Timing
(*{0.000105, {7, 1, 8, 2, 8, 1, 8, 2, 8, 4, 5, 9, 0, 4, 5, 2, 3, 5, 3, 6, 0, 2, 8, 7, 4, 7, 1, 3, 5, 2, 6, 6, 2, 4, 9, 7, 7, 5, 7, 2, 4, 7, 0, 9, 3, 6, 9, 9, 9, 5, 9, 5, 7, 4, 9, 6, 6, 9, 6, 7, 6, 2, 7, 7, 2, 4, 0, 7, 6, 6, 3, 0, 3, 5, 3, 5, 4, 7, 5, 9, 4, 5, 7, 1, 3, 8, 2, 1, 7, 8, 5, 2, 5, 1, 6, 6, 4, 2, 7, 4, 2, 7, 4, 6, 6, 3, 9, 1, 9, 3, 2, 0, 0, 3, 0, 5, 9, 9, 2, 1, 8, 1, 7, 4, 1, 3, 5, 9, 6, 6, 2, 9, 0, 4, 3, 5, 7, 2, 9, 0, 0, 3, 3, 4, 2, 9, 5, 2, 6, 0, 5, 9, 5, 6, 3, 0, 7, 3, 8, 1, 3, 2, 3, 2, 8, 6, 2, 7, 9, 4, 3, 4, 9, 0, 7, 6, 3, 2, 3, 3, 8, 2, 9, 8, 8, 0, 7, 5, 3, 1, 9, 5, 2, 5, 1, 0, 1, 9, 0, 1}}*)
