Only if they already have illicit access to the systems in question. In which case, considering Dropbox doesn't actually encrypt data at rest, it'd be much easier to get the data at the endpoints than in transit.
Not even remotely comforting. Talks all about how employees "are prohibited" from accessing your data, but that's unrelated to whether they're capable of doing so.
I much prefer the privacy policies of more secure services, which tend to say things like "we do not have the ability to access your data under any circumstances".