with this code, the \pi and \alpha disappear when \sffamily is active.
\documentclass{article}
\usepackage[warnings-off={mathtools-colon,mathtools-overbracket},math-style=french]{unicode-math}
\usepackage[default]{fontsetup}
\usepackage{siunitx}
\sisetup{%
text-family-to-math = true,%
text-series-to-math = true,%
}%
\begin{document}
2$\pi$ -- 3$\alpha$ --
\SI[parse-numbers=false]{2\pi}{\centi\meter} --
\SI[parse-numbers=false]{3\alpha}{\centi\meter}
{\bfseries
2$\pi$ -- 3$\alpha$ --
\SI[parse-numbers=false]{2\pi}{\centi\meter} --
\SI[parse-numbers=false]{3\alpha}{\centi\meter}
}
{\sffamily
2$\pi$ -- 3$\alpha$ --
\SI[parse-numbers=false]{2\pi}{\centi\meter} --
\SI[parse-numbers=false]{3\alpha}{\centi\meter}
}
{\sffamily\bfseries
2$\pi$ -- 3$\alpha$ --
\SI[parse-numbers=false]{2\pi}{\centi\meter} --
\SI[parse-numbers=false]{3\alpha}{\centi\meter}
}
\end{document}
with this code, the \pi and \alpha disappear when \sffamily is active.