Two things:
align
has a right-left alignment around &
while you want some elements to be centred;
align
inserts a large space between successive &
to separate equations.
I'd suggest alignat
with some box manipulations thanks to eqparbox
:

\documentclass{article}
\usepackage{amsmath,eqparbox}
\begin{document}
\begin{alignat*}{2}
2 \times (8 - 3) &= \eqmakebox[c1]{$2 \times 5$} & & \eqmakebox[c2]{} = 10, \\
2 \times (8 - 3) &= \eqmakebox[c1]{$2 \times 8 - 2 \times 3$} & {}={} & \eqmakebox[c2]{$16 - 6$} = 10.
\end{alignat*}
\begin{alignat*}{2}
6 \times ( 3 + 5 ) &= \eqmakebox[c3]{$6 \times ( 8 )$} & & \eqmakebox[c4]{} = 48, \\
6 \times ( 3 + 5 ) &= \eqmakebox[c3]{$6 \times 3 + 6 \times 5$} & {}={} & \eqmakebox[c4]{$18 + 30$} = 48.
\end{alignat*}
\end{document}
\eqmakebox[<tag>][<align>]{<stuff>}
aligns all <stuff>
(set in text mode) with the same <tag>
according to the specified <align>
ment (default is c
entre, otherwise it can be l
eft or r
ight).