The short answer is that 4B5B isn't a protocol you can use while I2C and SPI are.
I2C and SPI qualify as OSI Network level 1 and 2 specifications, covering both physical electrical specifications of connection between devices and how the connected devices use the connection to communicate. 4B5B is merely a bit encoding scheme, covering only how to represent 4 bits of data in 5 bits of signal to ensure that the resulting signal has adequate auto-clocking content. 4B5B is not a "protocol" or a level 1 or level 2 network specification, meaning that if you try to connect two devices "using 4B5B" you will still have far too many unspecified details to be able to actually create a connection over which you can exchange data.