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Genesis 3:13 And the Lord God said to the woman: Why hast thou done this? And she answered: The serpent deceived me, and I did eat. 14 And the Lord God said to the serpent: Because thou hast done this thing, thou art cursed among all cattle, and the beasts of the earth: upon thy breast shalt thou go, and earth shalt thou eat all the days of thy life. 15 I will put enmities between thee and the woman, and thy seed and her seed: she shall crush thy head,

The problem is that Pope Pius IX in Ineffabilis Deus (Latin for "Ineffable God") relies upon a Vulgate translation [and thus the Douay Rheims] of Gn. 3:15 which changed the “he” to “she shall crush thy head.”

However, as the Catholic Encyclopedia remarks:

"and I will put enmity between thee and the woman and her seed; she (he) shall crush thy head and thou shalt lie in wait for her (his) heel" (Genesis 3:15). The translation "she" of the Vulgate is interpretative; it originated after the fourth century, and cannot be defended critically. The conqueror from the seed of the woman, who should crush the serpent's head, is Christ…” (Catholic Encyclopedia, Immaculate Conception)

• In the Hebrew there is no “the” in “enmity between you and the woman” and it can refer to or include women in general and all women, (Gn. 14:16; Ex. 25:22; Est. 1:17) with the Lord speaking to Eve but including all women.

Note that the Neo-Vulgate (Nova Vulgata), the revised Latin version authorized by the Vatican, corrected the error and changed it from ipsa to ipsum in the Latin. (http://reformedapologeticsministries.blogspot.com/2012/02/catholic-misuse-of-genesis-315.html)

The approved notes in the official New American Catholic Bible (1970 ver.), while also allowing the Marian view, explains this verse,They will strike…at their heel: the antecedent for “they” and “their” is the collective noun “offspring,” i.e., all the descendants of the woman. Christian tradition has seen in this passage, however, more than unending hostility between snakes and human beings. The snake was identified with the devil (Wis 2:24; Jn 8:44; Rev 12:9; 20:2), whose eventual defeat seemed implied in the verse. Because “the Son of God was revealed to destroy the works of the devil” (1 Jn 3:8), the passage was understood as the first promise of a redeemer for fallen humankind, the protoevangelium. Irenaeus of Lyons (ca. A.D. 130–200), in his Against Heresies 5.21.1, followed by several other Fathers of the Church, interpreted the verse as referring to Christ, and cited Gal 3:19 and 4:4 to support the reference. http://usccb.org/bible/genesis/3

The Anglican/Roman Catholic International Commission explains the controversy:

“The Hebrew text of Genesis 3:15 speaks about enmity between the serpent and the woman, and between the offspring of both. The personal pronoun (hu’) in the words addressed to the serpent, “He will strike at your head”, is masculine. In the Greek translation used by the early Church (LXX), however, the personal pronoun autos (he) cannot refer to the offspring … but must refer to a masculine individual who could then be the Messiah, born of a woman. The Vulgate (mis)translates the clause as ipsa … This feminine pronoun supports a reading of this passage as referring to Mary which has become traditional in the Latin Church.

Even RC apologist Jimmy Akin also states,
Q: Please explain to me how come the Douay-Rheims Gen 3:15 and the New American Bible Gen 3:15 differ. I’m sure you know what I am talking about.

...The reason for the difference in the renderings is a manuscript difference. Modern translations follow what the original Hebrew of the passage says. The Douay-Rheims, however, is following a manuscript variant found in many early Fathers and some editions of the Vulgate (but not the original; Jerome followed the Hebrew text in his edition of the Vulgate). The variant probably originated as a copyist error when a scribe failed to take note that the subject of the verse had shifted from the woman to the seed of the woman... just as the first half of the verse, speaking of the enmity between the serpent and the woman, has been applied to Mary, the second half, speaking of the head crushing and heel striking, has also been applied to Mary due to the manuscript variant, though it properly applies to Jesus, given the original Hebrew. (www.jimmyakin.com/mary-and-genesis-315)

As a reformed source states, “He” .. in the original Hebrew is masculine. It is pronounced “hoo” and can also mean “it.” Many think it means “it” in reference to collective offspring of the woman crushing the head of the serpent. In the LXX, however, it is rendered autos “he,” indicating that the passage should be understood as a Messianic prophecy about Jesus Christ alone crushing the head. “He [Jesus] will crush the serpent’s head.” (http://reformedapologeticsministries.blogspot.com/2012/02/catholic-misuse-of-genesis-315.html)