It seems that the directory for the iOS Simulator has changed. It used to be in ~/Library/Application\\ Support/iPhone\\ Simulator/
and now it\'s in ~/Lib
Check this out:
As of Charles v3.9.3 there is an item in the Help menu, "Install Charles CA SSL Certificate in iOS Simulators", which will automatically install Charles's SSL CA certificate in your iOS Simulators.
Alternatively, you can change your code so that NSURLConnection accepts any SSL certificate. Please see the question and answer on Stack Overflow: How to use NSURLConnection to connect with SSL for an untrusted cert?
You can check it on this link: http://www.charlesproxy.com/documentation/faqs/ssl-connections-from-within-iphone-applications/