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Let \\(G_{K,S}\\) denote the Galois group of the maximal extension of \\(K\\) unramified outside \\(S.\\) This paper deals with the cup product map \\((\\ldotp , \\ldotp)_{S}: H^{1} (G_{K, S}, \\mu_{n} )^{\\otimes 2} \\rightarrow H^{2} ( G_{K, S}, \\mu_{n}^{\\otimes 2})\\) in the special case where its image is contained in the kernel of the localization map \\(H^{2} (G_{S, K}, \\mu_{n}^{\\otimes 2}) \\to \\bigoplus_{v \\in S} H^{2} ( G_{v}, \\mu_{n}^{\\otimes 2} ),\\) which is, by Poitou-Tate duality, isomorphic to \\(C_{K, S} \\otimes \\mu_{n},\\) \\(C_{K, S}\\) denoting the \\(S\\)-class group of \\(K.\\) The archetypal example is given by \\(n =\\) a prime \\(p\\), \\(K = {\\mathbb Q}(\\mu_{p}),\\) \\(S = \\{(1-\\xi_{p})\\},\\) the localization map being then the zero map.  The authors develop several formulae for the cup product \\((\\ldotp, \\ldotp)_{S}\\) in terms of ideals in a Kummer extension of \\(K\\) (Theorem 2.4), in terms of genus theory (Proposition 6.2) or (for \\(n= p)\\) in relation with the Hilbert symbol (Theorem 7.2). The situation being inherently nonlocal, interesting arithmetical consequences are expected. In particular, the induced pairing \\({\\mathcal O}^{\\otimes 2}_{K, S} \\to H^{2} ( G_{K, S}, \\mu_{n}^{\\otimes 2} )\\) gives rise to a canonical map \\(K^{M}_{2}( {\\mathcal O}_{K, S})/n \\to K_{2}({\\mathcal O}_{K, S})/n.\\) Restricting to the case \\(K = {\\mathbb Q}(\\mu_{p}),\\) \\(p\\) an odd prime satisfying Vandiver's conjecture, the authors conjecture that the natural map \\(K^{M}_{2} ({\\mathcal O}_{K, S}) \\otimes {\\mathbb Z}_{p} \\to K_{2}({\\mathcal O}_{K, S}) \\otimes {\\mathbb Z}_{p}\\) is surjective. Actually, for all irregular pairs \\((p, r)\\) (where \\(r\\) is even and \\(p\\) divides the Bernoulli number \\(B_{r}),\\) Vandiver's conjecture implies that the eigenspaces \\(A_{K}(\\omega^{p-r}) \\otimes \\mu_{p}\\) are cyclic, hence the ``cup product conjecture'' above is equivalent to the nontriviality of all pairings \\(\\langle \\ldotp, \\ldotp \\rangle_{r}\\) obtained by projecting \\((\\ldotp, \\ldotp )_{S}\\) on the eigenspaces. The authors use their Theorem 7.2 to derive a criterion which can be checked numerically for \\(p = 37\\) (the first irregular prime).  The cup product conjecture yields information on the form of relations in the maximal pro-\\(p\\)-quotient \\({\\mathcal G}\\) of \\(G_{K, S}.\\) In the Vandiver setting, these relations \\(\\rho\\) can be indexed by the irregular pairs \\((p, r),\\) and it is a matter of bookkeeping to write down an expression for \\(\\rho\\) in \\(\\text{gr}^{2} ({\\mathcal G})\\) in terms of values of \\(L_{p}\\)-functions (for the ``linear'' terms) and of the pairing \\(\\langle \\ldotp, \\ldotp \\rangle_{r}\\) (for the ``quadratic'' terms). For \\(p = 37,\\) one gets in this way an explicit nontrivial relation in \\(\\text{gr}^{2} ({\\mathcal G}).\\)  A related subject is the theory of the pro-\\(p\\)-fundamental group of \\({\\mathbb P}^{1} - \\{ 0, 1, \\infty\\}.\\) Deligne conjectures that \\(\\text{Lie}_{{\\mathbb Z}_{p}} ({\\mathcal G}) \\otimes {\\mathbb Q}_{p}\\) is free on certain distinguished elements, but the se\\-cond named author has shown that Greenberg's ``multiple conjecture'' (see below) implies that \\(\\text{Lie}_{{\\mathbb Z}_{p}} ({\\mathcal G})\\) itself is not free. The cup product conjecture gives nontrivial relations in \\(\\text{Lie}_{{\\mathbb Z}_{p}} ({\\mathcal G})\\) in terms of the pairing \\((\\ldotp, \\ldotp)_{S}.\\)  An Iwasawa-theoretic consequence of the cup product conjecture concerns Greenberg's multiple conjecture, which asserts that over the compositum \\(\\widetilde K\\) of all \\({\\mathbb Z}_{p}\\)-extensions of a number field \\(K,\\) the Galois group of the maximal \\((p)\\)-ramified Abelian pro-\\(p\\)-extension of \\(\\widetilde K\\) has no \\({\\mathbb Z}_{p} [[ G(\\widetilde K/K)]]\\)-torsion. By way of example, if \\(K = {\\mathbb Q}(\\mu_{p})\\) and the \\(p\\)-class group of \\(K\\) is cyclic, then the nontriviality of \\((\\ldotp, \\ldotp)_{S}\\) restricted to the cyclotomic units implies Greenberg's 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