Hi,
Upgrading vCenter during the day will cause an outage on centralized management services whilst it takes place. The connection/composer servers rely on vCenter to communicate with your VDI VM's so this would affect users ability to access them. In this particular case, I'm fairly confident that you would knock out the ability for people to connect to VM's and any provisioning activities that need to take place. However, users already connected should maintain their connection to the VDI desktop.
How do you deploy your VDI desktops: Full? Linked clones?
If this were me, I'd be planning on performing this upgrade out of hours.