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This from our kuler talk Adobe special guest, Ty Voliter:
The reason that the hue number of the HSB color model does not correspond to the angle on the wheel is because Kuler uses a red-yellow-blue color wheel. This wheel corresponds to the color wheel that many artists are familiar with where red/green, blue, orange, and magenta/yellow are complements. This wheel was invented by Johannes Itten, a Swiss color and art theorist. The color wheel does not correspond with the different types of color receptors in the human eye and instead reflects how pigments are mixed when painting. Adding a color's complement with this wheel mutes the color.
Here are some references with more info:
The kuler wheel is RYB from one viewpoint; from another, it approximates the RYGB circle quite well. That's what seems to be unique about it. It's not the classic Itten wheel -- it's been tweaked in an interesting way. It's not possible to come up with a good approximation of RYGB from Itten's wheel. It's also not possible to come up with a good approximation of RYB from, e.g., the NCS interpretation of the four-color RYGB wheel. That the kuler wheel seems to encompass both circles may suggest one reason why it's intuitive to work with.
It's not in keeping with the perceptual facts -- those are given by Munsell. But it is in keeping with the 'conceptual' facts -- i.e., the ways we think about color.