Very good question.
The reason simple: the coefficient $a_i$ for a variable $x_i$ in (single/multiple) regression is change in the expected value of the dependent variable $y$, for a unit change of variable $x_i$, keeping all other independent variables fixed.
That is: $a_i = \frac{\partial E[y|x_i]}{\partial x_i}$.
The specific case you are encountering, where correlation between $x_i$ and $y$ is 0, but its coefficient is statistically significant in multiple regression case can happen if you have a supressor variable: http://ericae.net/ft/tamu/supres.htm.
Here is a simple constructive example. Suppose I have three variables:
- $x \sim N(0,1)$
- $y \sim N(0,1)$
- $z = a\,x + b\,y + \epsilon$, where $a$ and $b$ are non-zero, and $\epsilon$ is some random independent noise.
Now consider the regression problem in which the predictors are $x$ and $z$, and the response variable is $y$.
Clearly, correlation between:
- $x,y$ is 0
- $x,z$ is non zero
- $y,z$ is non zero
Now, it's clear how $x$ can help improve $y$'s prediction accuracy even though it's uncorrelated with $y$. Informally, knowing $x$ helps subtract its component in $z$, which helps boost the residual signal in $z$ that can predict $y$.