Travel question - Cinque Terre to Munich

Use this website to see for your train options. Use a nearby date as it will not show any trains for September, 2022.
https://www.bahn.com/en

There are schedule changes in December and June every year. There may be more trains by then, but currently it is 11 1/2 hour journey by train.

Lufthansa has direct flights to Munich from Genoa. It is 3 hours by train and shuttle bus from Monterosso to Genoa Airport. Arrive 2 hours before the 2 pm flight, 1 hour in the air and 1 1/2 hour from arrival until you are in central Munich, that is 7 1/2 hours flying.

You can also use the website Rome2Rio, plug in where you want to go and it will give you different solutions. I used this website to plan most of most journeys in Europe.

Just for fun I plugged in your trip and it recommended as the fastest take a train to Florence (6 hours/43 min) with a connection in Pisa then fly.

There are also overnight trains from both Milan and Florence to München.

Is it possible to re-arrange the order (i.e., Cinque Terre before Florence) to end in Florence and then fly?

Another option is to take a direct train from Monterosso to Genoa (Genova Piazza Principe; 1h 30m) and then a train to Genova Sestri Ponente Aeroporto (15-minutes) and then another train to Genova Aeroporto C. Colombo (15-minutes) and fly non-stop to Munich on Lufthansa. I see fares starting at $102 on Skyscanner.
You can also take a direct train from Monterosso to Milano Centrale (3h) and take the overnight train to Munich. I would definitely reserve a sleeper car for that leg of the trip. The latter would be my preferred option, plus you can store your luggage at the station while you sightsee: https://stasher.com/luggage-storage/milan/milan-central-station.

I like the idea above of taking the direct train from Monterosso to Milano Centrale, and from there either the overnight train to Munich, or take an express train to Malpensa airport and fly to Munich. I think there is another airport near Milan as well but can't recall the name. We took the direct train from Milano Centrale to Monterosso in 2019 and got the first class tix with reserved seats and found it enjoyable. Look on trentitalia.com about six months before your ride for pricing and departure times.

It really does not make any sense to go all the way to Milan, then a train of nearly 1 hour, to get to Milan Malpensa for a 1 hour flight to Munich. Trenitalia shows trains to Genoa Sestri Ponente, then a 5 minute shuttle bus ride to the airport for a 1 hour flight to Munich.

This website lays out the options....

https://www.rome2rio.com/map/Monterosso-al-Mare/Munich

I've found that it's reasonably accurate most of the time, but it's also a good idea to double check transportation connections on either the rail or airline websites, as schedules do change.

Despite the fact that it will probably be a longer trip, my preference would still be to travel by train as I detest the usual airport hassles with check-in, security, cramped seating and possibly expensive baggage charges. Although the actual flight may only be an hour, it's also necessary to include time to & from airports, waiting for flights, boarding & deplaning, etc. I've found the total time can be six hours or more.

If I were making that trip, I'd probably use a train departure from Monterosso at 06:54, arriving Munich Hbf at 18:27 (time 11H:33M, 3 changes). I find travel by rail to be a more relaxing and pleasant trip and I enjoy seeing the scenery.

and using the train is MUCH better for the environment

I find travel by rail to be a more relaxing and pleasant trip and I
enjoy seeing the scenery.

And since this is a trip that crosses the Alps, the scenery will be far from boring.

If you have the time do the train all the way!

Thanks to everyone for the helpful information :)