Here are a couple of examples. I included a non-portrait at the same location because the sunset was a bit brighter. I then move on to photograph my girlfriend, but the sunset had almost disappared. They aren't great, as I had only had the camera for three months so was still operating in numpty mode (Program). The key thing to consider is that you are mixing two different exposures - one for the background, metered in the usual way, and one for the subject, which will be illuminated by the flash.
To tone down the sky I dialled in some negative EC (-1.33 stops in the first example and -2 stops in the second) to drop the overall exposure, thus darkening the background and the subject. I let the flash (580EX) run an ETTL2 mode with 0 FEC and that filled in the subject quite nicely in each shot.
A bit of experimentation was required in order to get the balance right (well, as I wanted it). In the first example there is no PP except sharpening. In the second I did bring up the levels by 0.5 stops in DPP. Now that 18 months have passed since taking these, I would approach the challenge just a little differently. I would use manual exposure to fix the background brightness to suit, regardless of the exact composition and position of the sun, and I would quite happily ride the FEC until I got things just perfect. I would also pay momre attention to the RGB histogram than I did back then, in order to verify my levels properly.
Exif data is in the images.
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