Sirs
Bugatti EB110 GT (one of my favorites) was probably the first to use 5 valves in 1990, though Peugeot GP racer is using the design in supercar racing in 1921.
1924 Bugatti Type 18 was probably the first to use 3 valve.
Honda S600 probably was the one to pioneer 4 valve in 1964.
Toyota adopted 4V from Lotus in late 1980's, I think.
The Original A4 was probably the first commercial car to use 5v in 1995, Mitsubishi and Yamha also did experiments on that.
Ferrari has admitted afterwards that 5v is too costly and complex and converted to 4V.
Regards