It may help if you compare const char** glfwExtensions; with the famous variable argv in main:
int main(int argc, char **argv) //  or:  char *argv[]
glfwExtensions can likewise be seen as an array of const char*
So, after
glfwExtensions = glfwGetRequiredInstanceExtensions(&glfwExtensionCount);
you can therefore
for(uint32_t i = 0; i < glfwExtensionCount; ++i) {
    // access   glfwExtensions[i]    here
    // or     *(glfwExtensions + i)  (same thing)
}
Since glfwExtensions is a const char**, then glfwExtensions + i is also a const char**, i steps from glfwExtensions + 0.
The asterisk in *(glfwExtensions + i) means that you dereference the pointer to get a reference to the value it's pointing at - which, since you have a const char**, is a const char*.
glfwExtensions is a pointer to the first element in glfwExtensionCount number of elements and you can use glfwExtensions + i to get a pointer to any of those elements.
The line you wonder about
std::vector<const char*> extensions(glfwExtensions,
                                    glfwExtensions + glfwExtensionCount);
is using the vector constructor that takes two iterators and populates the vector with the dereferenced values, the actual const char*s.
glfwExtensions + glfwExtensionCount is pointing one element past the last element. You are only allowed to deference the elements in the range [glfwExtensions + 0, glfwExtensions + glfwExtensionCount - 1] so this pointer is used to tell the vector where to stop reading values.
It's similar to doing this:
const char** current = glfwExtensions;
const char** one_past_last = glfwExtensions + glfwExtensionCount;        
std::vector<const char*> extensions;
extensions.reserve(std::distance(current, one_past_last));
for(;current != one_past_last; ++current) // stop at one_past_last
    // dereference current to get the value it is pointing at:
    extensions.push_back(*current);