HUD Color Picker

In Photoshop CS5 and newer, you can use the HUD Color Picker. With the brush tool selected, hold Alt Shift Right-Click (macOS: Control Option Command Click).

You can hold the Spacebar to lock the color while you move over to the right to change the saturation, let go of the Spacebar and move up and down.

HUD Color Picker

 

If you would rather use the color wheel HUD Color Picker then first go to Edit > Preferences > General (or Press Ctrl K), and in the HUD Color Picker drop-down select Color Wheel. Then follow the keyboard combination described above to get the Wheel HUD Color Picker.

Wheel HUD Color Picker