I DON'T think so. its not possible while insert
but you can do while select the above record you can do it like this
create table Satheesh(fieldid int identity(1,1), names varchar(20), rollno int)
insert into Satheesh values('Santhosh',1)
insert into Satheesh values('Govind',2)
insert into Satheesh values('Nikhil',3)
insert into Satheesh values('divya',4)
select row_number() over (order by names) as rollno, names from satheesh
order by names
result
rollno names
-------------------- --------------------
1 divya
2 Govind
3 Nikhil
4 Santhosh
(4 row(s) affected)