Blue is already there, and easy to get more of. White LEDs are based on blue LEDs, generally 450nm, which is very close to the chlorophyll ideal, and close enough to UVA to trigger most plants', "I'm getting a lot of summer sun, so need to stay bushy and produce oils, terpenes, etc.," responses. The higher the CCT, the more of that native blue is left (CCT *generally* correlates well with blue:red ratios). So, using 5000K instead of 3500K would be equivalent to adding more blue, I think on the order of +20%, but don't quote me on the relative amount. In addition, blue LEDs under about 440nm have low efficiency and efficacy, so more 450nm tends to be more cost-effective than closing in on 430nm.
Meanwhile, because most 80 CRI white LEDs (all the common ones, today) peak so far away from 660-680nm, some peaking as low as 620nm, specifically adding 660nm can be more efficient than going further down in CCT to get more red for chlorophyll A. Chlorophyll B's response curves are a good match for many white LEDs, from the start, especially those with lots of red around 640nm. The Samsung's, FI, almost all have their red-orange peak around 620nm, which is low for chlorophyll A and B.
Then, looking at it more from the angle of the McCree curve, the red hump is severely low in most white LEDs, compared to the McCree response curve, which gets very active towards 700nm, as the white LEDs' outputs are trailing off, while the green and blue ranges aren't so bad off (and are easy to adjust for with emitter selection). Adding more energy alone works, but also increases energy that the plant must get rid of as heat. Absorption of, "close enough," frequencies is less efficient, and the energy not used for chemical reactions has to go somewhere.