PPTP actually uses GRE (generic routing encapsulation).
Originally Microsoft developed PPTP (along with a few other vendors) while Cisco pushed a protocol called L2F which was primarily implemented in Cisco products. A combination of the best features of PPTP and L2F was formed to create L2TP.
L2TP (Layer Two Tunneling Protocol) supports non-TCP/IP clients and protocols (such as Frame Relay, ATM and SONET) but fails to define any encryption standard. That's why L2TP is used with IPsec. It is also important to note that IPsec is more resource intensive than PPTP, hence the overhead with a L2TP solution is higher than PPTP.
PPTP is also somewhat easier to get up and running. IPsec does not use DES or 3DES at all. It is a combination of a couple of seperate protocols (AH and ESP).
Authentication Header (AH): provides authenticity guarantee for packets, by attaching strong crypto checksum to packets.
Encapsulating Security Payload (ESP): provides confidentiality guarantee for packets, by encrypting packets with encryption algorithms
Although L2TP (Layer 2 Tunneling Protocol) is compatible with most network protocols it is not widely deployed but is common in certain Telco and ISP networks.
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