Acredito que um gatilho de logon deve funcionar:
CREATE OR REPLACE TRIGGER db_logon
AFTER logon ON DATABASE WHEN (USER = 'A')
BEGIN
execute immediate 'ALTER SESSION SET CURRENT_SCHEMA = B';
END;
CREATE OR REPLACE TRIGGER db_logon
AFTER logon ON DATABASE WHEN (USER = 'A')
BEGIN
execute immediate 'ALTER SESSION SET CURRENT_SCHEMA = B';
END;