The scope shows the debug output pin set on compare and reset on EOC - but the conversion is actually started just before that with the PWM positive edge (as cited in previous post), not as intended on compare.
Achieving the intended timing with CC2 seems to require it to be set to generate a rising edge to start AD conversion:
The timer output TIM1_CH2 is an alternate function on PA9, conflicting with USART1_TX.
This would mean that there is no ''internal signal'', and that the reference manual is misleading in describing it as such:
TIM1_CC2 event
Internal signal from on-chip timers
I could not find further information about this mysterious internal connection. The only mentions of ''