Firstly, there's one big thing that screams out at me looking at that screenshot, and that's the text Wow6432Node
in the middle of your registry key's path.
From MSDN: 32-bit and 64-bit Application Data in the Registry
On 64-bit Windows, portions of the registry entries are stored
separately for 32-bit application and 64-bit applications and mapped
into separate logical registry views using the registry redirector and
registry reflection, because the 64-bit version of an application may
use different registry keys and values than the 32-bit version.
...
Redirection subnodes in the registry tree are created automatically by
the WOW64 component using the name Wow6432Node. As a result, it is
essential not to name any registry key you create Wow6432Node.
On a machine running 64-bit Windows, the Wow6432Node
is the part of the registry that 32-bit applications are silently redirected to (without the app realising).
The way to access this redirection in SCCM's registry detection is to let SCCM be redirected in the same way that the application is by ticking the "This registry key is associated with a 32-bit application on 64-bit systems" box that you can see near the middle of your screenshot, and deleting the \Wow6432Node
out of your registry key's path. This means that SCCM now knows that this registry key is found in the 32-bit registry section and will look there for it whether you're on a 32- or 64-bit machine.
Secondly, I don't know your application, but it is very possible that there is an easier way to do this detection.
Although the app is an EXE, it is entirely possible (and very, very common) that the EXE is just a wrapper around a Windows Installer MSI, in which case you can use the "Windows Installer" Product Code detection method very easily.
There are a few ways to find the MSI product code of an EXE by just checking on the test machine that you've already installed the app on. One way is to use the WMI command line interface to list the installed apps and their installer codes, from a DOS prompt run:
wmic product get Name, IdentifyingNumber
If your app shows up in that list with an "Identifyingnumber" then you should be able to put that into the Windows Installer detection method.