The role of the longest element in $W$ emerges only gradually in the Chevalley structure theory.  This is developed similarly but in slightly different styles in the three books with the same title *Linear Algebraic Groups* (by Borel, Springer, and me).
It's important to understand that the desired statement about opposite Borel subgroups of a reductive group depends on a long series of steps culminating in the Bruhat decomposition.   In my book, the later steps occupy Sections 26-28.
There's already a proof in 26.2 of the existence of a (necessarily unique) Borel subgroup intersecting a given Borel subgroup $B$ in a specified maximal torus $T$ of $B$.   Theorem 26.3(b) almost gives the answer you want, but before enough details of the structure theory are in place.   The underlying strategy is to fix $B$ and the flag variety $G/B$, then see that the fixed points of $T$ on the latter are in natural bijection with both the elements of $W$ and the Borels containing $T$.    (I don't think this got articulated explicitly enough, however.)    
   
Only in my Section 27 is the root system explored, followed in Section 28 by the full details of the Bruhat decomposition.    There is still some work to be done 
on the internal structure of $W$ (including the length function and longest element) in relation to the root system.    In my treatment this gets folded into the more general study of $BN$-pairs (Tits systems), which axiomatize the Bruhat decomposition efficiently.   Along the way it turns out for instance that $W$ has a natural structure of Coxeter group.    

Unfortunately, the precise statement you want to see a proof of is left somewhat implicit in all these textbook treatments.   But this is due partly to the fact that so much heavy theory has to be developed systematically before that kind of statement becomes obvious.   It's hard to take any real shortcuts, but also unnecessary to get into the theory of buildings and such.