I don't know of anything as bare hands as the proof that pi1(G) must be abelian, but here's a sketch proof I know (which can be found in Milnor's Morse Theory book. Plus, as an added bonus, one learns that pi3(G) has no torsion!):
First, (big theorem): Every (connected) Lie group deformation retracts onto it's maximal compact subgroup (which is, I believe, unique up to conjugacy). Hence, we may as well focus on compact Lie groups.
Let PG=f:[0,1]rightarrowG|f(0)=e (I'm assuming everything is continuous.). Note that PG is contracitble (the picture is that of sucking spaghetti into one's mouth). The projection map pi:PGrightarrowG given by pi(f)=f(1) has homotopy inverse OmegaG=Loop space of G = finPG|f(1)=e.
Thus, one gets a fibration OmegaGrightarrowPGrightarrowG with PG contractible. From the long exact sequence of homotopy groups associated to a fibration, it follows that pik(G)=pik−1OmegaG
Hence, we need only show that pi1(OmegaG) is trivial. This is where the Morse theory comes in. Equip G with a biinvariant metric (which exists since G is compact). Then, following Milnor, we can approximate the space OmegaG by a nice (open) subset S of Gtimes...timesG by approximating paths by broken geodesics. Short enough geodesics are uniquely defined by their end points, so the ends points of the broken geodesics correspond to the points in S. It is a fact that computing low (all?...I forget)* pik(OmegaG) is the same as computing those of S.
Now, consider the energy functional E on S defined by integrating |gamma|2 along the entire curve gamma. This is a Morse function and the critical points are precisely the geodesics**. The index of E at a geodesic gamma is, by the Morse Index Lemma, the same as the index of gamma as a geodesic in G. Now, the kicker is that geodesics on a Lie group are very easy to work with - it's pretty straight forward to show that the conjugate points of any geodesic have even index.
But this implies that the index at all critical points is even. And now THIS implies that S has the homotopy type of a CW complex with only even cells involved. It follows immediately that pi1(S)=0 and that H2(S) is free (H2(S)=mathbbZt for some t).
Quoting the Hurewicz theorem, this implies pi2(S) is mathbbZt.
By the above comments, this gives us both pi1(OmegaG)=0 and pi2(OmegaG)=mathbbZt, from which it follows that pi2(G)=0 and pi3(G)=mathbbZt.
Incidentally, the number t can be computed as follows. The universal cover tildeG of G is a Lie group in a natural way. It is isomorphic to a product HtimesmathbbRn where H is a compact simply connected group.
H splits isomorphically as a product into pieces (all of which have been classified). The number of such pieces is t.
(edits)
*- it's only the low ones, not "all", but one can take better and better approximations to get as many "low" k as one wishes.
**- I mean CLOSED geodesics here
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