First create the custom attribute class:
[AttributeUsage(AttributeTargets.Property, AllowMultiple = false, Inherited = true)]
public class UniqueAttribute : ValidationAttribute
{
   public override Boolean IsValid(Object value)
    {
        // constraint implemented on database
        return true;
    }
}
Then add to your classes:
public class Email
{
    [Key]
    public int EmailID { get; set; }
    public int PersonId { get; set; }
    [Unique]
    [Required]
    [MaxLength(100)]
    public string EmailAddress { get; set; }
    public virtual bool IsDefault { get; set; }
    public virtual Boolean IsApprovedForLogin { get; set; }
    public virtual String ConfirmationToken { get; set; }
    [ForeignKey("PersonId")]
    public virtual Person Person { get; set; }
}
Then add a Initializer on your DbContext:
public class Initializer : IDatabaseInitializer<myEntities>
{
    public void InitializeDatabase(myEntities context)
    {
        if (System.Diagnostics.Debugger.IsAttached && context.Database.Exists() && !context.Database.CompatibleWithModel(false))
        {
            context.Database.Delete();
        }
        if (!context.Database.Exists())
        {
            context.Database.Create();
            var contextObject = context as System.Object;
            var contextType = contextObject.GetType();
            var properties = contextType.GetProperties();
            System.Type t = null;
            string tableName = null;
            string fieldName = null;
            foreach (var pi in properties)
            {
                if (pi.PropertyType.IsGenericType && pi.PropertyType.Name.Contains("DbSet"))
                {
                    t = pi.PropertyType.GetGenericArguments()[0];
                    var mytableName = t.GetCustomAttributes(typeof(TableAttribute), true);
                    if (mytableName.Length > 0)
                    {
                        TableAttribute mytable = mytableName[0] as TableAttribute;
                        tableName = mytable.Name;
                    }
                    else
                    {
                        tableName = pi.Name;
                    }
                    foreach (var piEntity in t.GetProperties())
                    {
                        if (piEntity.GetCustomAttributes(typeof(UniqueAttribute), true).Length > 0)
                        {
                            fieldName = piEntity.Name;
                            context.Database.ExecuteSqlCommand("ALTER TABLE " + tableName + " ADD CONSTRAINT con_Unique_" + tableName + "_" + fieldName + " UNIQUE (" + fieldName + ")");
                        }
                    }
                }
            }
        }
    }
}
And for last add the Initializer at Application_Start inside Global.asax.cs
System.Data.Entity.Database.SetInitializer<MyApp.Models.DomainModels.myEntities>(new MyApp.Models.DomainModels.myEntities.Initializer());
That's it. based on the vb code at https://stackoverflow.com/a/7426773