fs.readFile takes a call back which calls response.send as you have shown - good. If you simply replace that with fs.readFileSync, you need to be aware it does not take a callback so your callback which calls response.send will never get called and therefore the response will never end and it will timeout.
You need to show your readFileSync code if you're not simply replacing readFile with readFileSync.
Also, just so you're aware, you should never call readFileSync in a node express/webserver since it will tie up the single thread loop while I/O is performed. You want the node loop to process other requests until the I/O completes and your callback handling code can run.