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I am assuming you are referring to the US Constitution. The U.S. Constitution uses but does not define the phrase "natural born Citizen".
Based on the current event, sure would have been helpful had the drafters taken some time to tell us what they intended by that phrase. The consensus from "case law" (courts interpreting this phrase) is that natural-born citizens include, subject to exceptions, those born in the United States
The leading case is came from the Supreme Court in 1939, where it stated in its decision in Perkins v. Elg, that a person born in America and raised in another country was a natural born citizen, and specifically stated that they could "become President of the United States"
In 1951, the U.S. Court of Appeals for the Tenth Circuit noted in Zimmer v. Acheson that "[t]here are only two classes of citizens of the United States, native-born citizens and naturalized citizens" The court ruled that Zimmer, who was born abroad in 1905 to a U.S. citizen father and a noncitizen mother, was himself a citizen under the nationality law in force at the time of his birth, but "his status as a citizen was that of a naturalized citizen and not a native-born citizen".
In 1961, the U.S. Supreme Court ruled in Montana v. Kennedy that an individual who was born in 1906 in Italy to a U.S. citizen mother and a noncitizen father was not a U.S. citizen by birth under the nationality laws in force at the time of his birth. It observed that automatic citizenship was granted to children of U.S. citizen fathers and noncitizen mothers by a 1855 act of Congress, but the reverse situation was only addressed, non-retroactively.
In 2010, a three-judge panel of the United States court of appeals for the Fifth Circuit held that natural born citizens can lose their citizenship if their territory of birth later ceases to be U.S. territory. The case involved a Philippine-born litigant who could not claim U.S. citizenship on the basis of his parents, who lived all their lives in the Philippines, because they were born while the Philippines was U.S. territory prior to being given its independence.
So, as far a Rubio goes, since Puerto Rico is still US territory, there is support that he meets the definition of natural born.
There is no Supreme Case directly on point...so no case that holds he meets that definition (that of natural born citizen)
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