The correct answer is option 3: Annual Financial Statement.

In the Indian parliamentary system, the Rajya Sabha is one of the two houses of the Parliament, with the other being the Lok Sabha. The Rajya Sabha represents the states and union territories of India.

Constitutional Amendment (option 1) can be introduced in the Rajya Sabha because it requires the approval of both houses of Parliament, with a special majority.

CAG Report (option 2) can be introduced in the Rajya Sabha because it is a document that presents the findings and recommendations of the Comptroller and Auditor General of India.

A Bill to alter the boundaries of any State (option 4) can also be introduced in the Rajya Sabha because it is a legislative proposal to modify the boundaries of a state.

However, the Annual Financial Statement (option 3) cannot be introduced first in the Rajya Sabha. The Annual Financial Statement, commonly known as the budget, is presented by the Union Finance Minister in the Lok Sabha, the directly elected house of Parliament. The Rajya Sabha does not have the power to introduce or pass the budget.

Therefore, option 3 is the correct answer.