Technically, yes, you can lean an extension ladder directly against a gutter, but I generally wouldn't recommend it. Here's why...
When you boil it right down, your house only has 8 things you REALLY need it to do for you. It might sound simplistic to boil it down like this, but I like to think of it as getting to the first principles of a house.
These dark gray stripes running down the front of gutters due to molecular bonding of pollutants to the aluminum. Here's what to do to get rid of them.