@Rishi Verma • Thank you for reaching out.
Unfortunately, if the Web App can only be accessed via routing the request through VNet, you will not be able to call that web app/API via B2C. I assume that the B2C custom policy will make a REST call to the Web App via RESTful technical profile, in case of which the request is directly made via the internet and the API must be publicly accessible. You will have to secure the API by implementing authentication for API. You can then acquire the token via RESTful TP as mentioned in this XML snippet and pass that token in the authorization header to call the API.
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@Rishi Verma • I have not tested it out but It should work with below-mentioned setup:
B2C--> Frontdoor--> routingrule/Backendpool--> Application Gateway -->Backendpool --> ASE (Inside VNET)
You need to add App Gateway as Front Door cannot directly route within a virtual network, as documented here
Thanks @AmanpreetSingh-MSFT - Yes we do have an ILB (Application Gateway) after Frontdoor to route traffic inside VNET.
Thanks once again for all the clarifications.