The earliest reference I know about is Wendt, H. Die gordische Auflösung von Knoten. Math. Z. 42, 680–696 (1937) It's been a very long time since I read this paper (and my German is mediocre, so it would take some effort for me to re-read it today), so I can't remember if it references anything else. As evidence that this is the original source, Reidemeister's classic [book][1] on the subject references Wendt's paper when it introduces the unknotting number. See the beginning of Chapter 2. [1]: https://www.maths.ed.ac.uk/~v1ranick/papers/reidemeister_eng.pdf