You were right EricSo fault unlikely to be valve.
Recap ...
System Boiler, Three way valve, Nest Controls
Schedule ... 6am to 7am HW alone ... 7am to 8am CH alone
Problem was ... The last few days the HW hasn't kicked in at 6am but would if boost option was used.
Same again this morning, no HW response ... boosted for 30 mins at 0645.
The CH came on at 0700, noticed the rads got up to normal temperature.
(Always imagined the HW would take away from the CH)
Boosted again at 0715 ( The HW has been normal temp all day)
Set a new HW schedule for 4pm and stood at the side of the boiler ... nothing happened ... not a sound.
Assumed the problem was with the Nest or the connection between my phone App and the thermostat.
Checked the schedule on the wall mounted Nest Thermostat and found the extra 4pm one was showing ruling out the App
During the course of checking all the settings on the thermostat dial I found the problem ... " Water Schedule Disabled !!! "
Sorry to have troubled you and thank you all again for your help
Ray