Grant execute on all stored procedures in a database including system procs to a user or role.

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use [MyDatabase];
grant execute to [MyDomain\MyUser];
grant execute to [MyCustomDatabaseRole];

Grant execute on all stored procedures in a schema in a database to a user or role.

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use [MyDatabase];
grant execute on schema::dbo to [MyDomain\MyUser];
grant execute on schema::dbo to [MyCustomDatabaseRole];

Grant execute on a single stored procedure to a user or role.

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use [MyDatabase];
grant execute on object::dbo.MyStoredProcedure to [MyDomain\MyUser];
grant execute on object::dbo.MyStoredProcedure to [MyCustomDatabaseRole];