- Just look at the datasheet (the RM doesn't list pin functions): there is a USARTx_CK pin only for USART1/2/3 and no _CK pin for any other UART. So at least the clock out pin is only available for USART1 to 3, which is kind of end of the story? (Even if internally all UARTs are the same IP, there's no point in enabling the sync mode for those who can't route the CK signal to any pin.)
- As to using USARTs as SPI, from what I can tell, it still generates start and stop bits but those are generated without the clock apparently, so unless you require a specific level for the data pins when data is not clocked, you could indeed used them as just SPI, only that the throughput will not be completely continuous as opposed to multi-byte SPI, having those pauses for the start and stop bits. (Maybe you can disable them, but haven't seen that.)
They don't seem to allow generating the clock permanently, which could actually be useful in conjunction with a synchronous transmitter with start and stop bits (the start and stop bits acting as framing without the need for an extra CS pin), and some slave devices could benefit from a permanently on clock (something I've already used).