I think, the only way to add a shortcut for "Use grayscale" is to create an Applescript, that will be launched by a 3rd Party Hotkey-Manager application like Butler, Quicksilver or others.
Because you can´t script the "Universal Access" pane directly, you have to realize it with a special kind of Applescript, called UI-Scripting.
So first of all, if you will give it a try, open "Universal Access" and "enable access for assistive devices". This will be necessary to make UI-Scripting work!
I do not know the correct Applescript terminology, but this will work:
tell application "System Preferences"
activate
reveal first anchor of pane "com.apple.preference.universalaccess"
delay 1
tell application "System Events"
tell process "System Preferences"
keystroke tab
keystroke tab
keystroke tab
keystroke tab
keystroke tab
keystroke tab
keystroke tab
keystroke space
end tell
end tell
quit
end tell
Most of this 3rd Party apps like Butler can run this Applescript directly.
Or open the script in ScriptEditor.app and save it as an application(-bundle). Drag this application then to your dock and run it from there.
Spażek