Again, overkill; but, for what it's worth, here's a tikz solution that appears to work.

The primary difficulty here, as elsewhere, was getting the underbrace and its text to count for vertical spacing, but not until after the outer parentheses were set. The tikz solution I initially had in mind was to save the position with tikz nodes in the middle of the math, and then come back afterwards with an underbrace at the saved position. The trouble with this approach is that tikz constructions that reference positions from other tikz pictures are supposed to be given the overlay option, which effectively smashes any effect the construction would have on the vertical spacing (and would make the next line too high).
The way I got around this was to put the entire expression in a node in a tikz picture. Thus, I actually have tikz nodes inside a tikz picture inside a tikz node inside a tikz picture. I'm not sure whether this behavior is supported, but it seems more or less to work for this particular construction.
\documentclass{article}
\usepackage{amsmath,tikz}
\usetikzlibrary{decorations.pathreplacing}
\usetikzlibrary{calc}
\newcommand{\currentmatrix}{}
\newcommand{\tikznode}[2][$\currentmatrix$]{\tikz[overlay]\node (#2) {\vphantom{#1}};}
\begin{document}
\renewcommand{\currentmatrix}{\begin{pmatrix} 1 & 2\\ 3 & 4 \end{pmatrix}}
\begin{align*}
\tikz[remember picture,baseline=(left.east),inner xsep=0pt]{
\node {$\exp \left(\gamma \tikznode{left}
\begin{pmatrix} 1 & 2\\ 3 & 4 \end{pmatrix}\tikznode{right}
\right)$};
\draw[overlay,decorate,decoration={brace,amplitude=3pt}]
($(right.south west) + (0,4pt)$) --
coordinate(texthere) ($(left.south east)+(0,4pt)$);
\path (texthere) node[below] {$\scriptstyle\text{some text}$};
} &= e^{\gamma A} \\
&= \exp(\gamma A)
\end{align*}
\end{document}
\Biggl(for the left parenthesis and\Biggr)for the right (they deal better with spacing). And works withbig,Big,… – Manuel Dec 11 '12 at 21:17\biggl(and\biggr)that match the inner parentheses. – barbara beeton Dec 11 '12 at 21:30\underbracenot in the parenthesis. – Manuel Dec 11 '12 at 21:32