Unfortunately not. Rather than a long post, have a look at reg 21AA IS regs and the commentary on page 304 of the 2007 Soc Sec leg vol 2. The relevant HB provisions are in reg 10 HBR, but they say the same thing for your purpose.
Basically, the claimant must be a 'qualified person', which includes workers. In the case of A8 and A2 nationals, the definition of qualified person is modified such that they must be properly registered whilst in work, or otherwise exempt from registration.
I've seen a few cases where exemption hasn't been spotted by DWP, so always worth checking.
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