What I've done for a few people is to create a batch file that runs calibre and after calibre exits, runs the sync to DropBox (or other cloud provider). I looked at the sync before opening calibre but decided that since—in theory—the calibre library on the local computer and the cloud provider were synced from the last run, that syncing before starting calibre was not necessary. Also, most people didn't seem to mind a task running for a few minutes after exiting calibre but they were not happy with calibre taking that many minutes to start up.
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