I would proceed with caution. Lets say you are interested in working for company x. Here is a list of possible actions.
Best: someone in your first degree network works there and you ask them some questions about the position and if they thought it would be a good fit for you.
Good: someone in your second degree network works at company x (IE friend of friend) and you ask your first degree network connection (your actual friend or connection) for an introduction so you could ask if you are possibly a good fit for company x.
OK: you reach out to directly to someone in your second degree network, saying you are a friend of a friend, tell them of your interest in working for company x, and ask them to take a look at your work to give their opinion on if you might be qualified.
Not Good: you reach out to second and third degree connections directly and ask them to recommend you for the job.
Bad: you carpet bomb everyone that works at company x with invites telling them why they should hire you. They will probably talk about it… I’ve seen it happen and the results are not good.