You might be able to persuade a FTDI-style USB device to bit-bang 10base2 Ethernet for you. You'd implement a "PHY" side which translates the wire traffic to a clean bitstream and aligns the frame start and then just have the PC handle all of it in software for you.
In practice today, if you have a DB9 serial port, that goes into the section of the chipset which is concerned with all the "legacy" interfaces, which ultimately turns up on the PCIe bus like everything else.
> I think that approaching this from a security angle is a quick road to madness
Yes.
Regarding USB: CDC-NCM isn't hard to implement in any MCU but implementing a USB HS PHY basically requires ASIC hardware.
If you use a $0.30 USB HS ULPI PHY, one could implement USB CDC-NCM in an FPGA pretty easily.