I haven't experienced them all personally, but I know the VS Upper Class is considered quite good, the BA Club Class (with which I have alot of personal experience) is decent although they cram in alot of seats, and CO BusinessFirst has won some awards. Haven't seen AA's 777 business class but it's supposed to be ok, certainly better than what they have on the 767 they operate to other European cities from JFK.
I think the opportunity has less to do with poor onboard service at the majors than with exclusivity, customization of the experience and less airport hassle when flying with a smaller number of people. For example, Eos was allowing a very short check in time and for people to pretty much carry on all of their baggage but not sure how the new security restrictions will affect this.
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