You can directly create 32 random bytes to be your private key. Example below. But it is VERY important: these 32 bytes must be from cryptographically-secure pseudorandom generator. For example, if you use C# built-in Random class, anyone will be able to restore your private keys with regular computer. You need to be very careful if you plan to use this in real bitcoin network. I am not sure if Guid generation is cryptographically-secure.
static void Main(string[] args)
{
byte[] GetRawKey()
{
// private key=1 in this example
byte[] data = new byte[32];
data[^1] = 1;
return data;
}
var key = new Key(GetRawKey()); // private key
var pair = key.CreateKeyPair(); // key pair (pub+priv keys)
var addrP2pkh = key.GetAddress(ScriptPubKeyType.Legacy, Network.Main); // P2PKH address
var addrP2sh = key.GetAddress(ScriptPubKeyType.SegwitP2SH, Network.Main); // Segwit P2SH address
Console.WriteLine(addrP2pkh.ToString());
Console.WriteLine(addrP2sh.ToString());
}