Arnaud Clement beat British teenager Andy Murray 7-6, 6-2 to win the Legg Mason Classic.
The world number one repeated his Australian Open final victory over Marat Safin with a 7-6, 7-6 win to reach the second round of the Dubai Open.
Spaniards David Ferrer and Juan Carlos Ferrero also suffered first round shocks at the Valencia Open on Tuesday.
Holders Croatia had to be content with a win and a loss from the opening day's two singles rubbers in the Davis Cup.
Andre Agassi slumped to a 7-5, 7-5 defeat against Bjorn Phau at the Dubai Open
Israel reached the Davis Cup semi-finals for the first time on Saturday after Andy Ram and Jonathan Erlich gave them an unbeatable 3-0 lead over Russia in their World Group quarter-final.
Argentine Guillermo Coria and Russia's Nikolay Davydenko are front-runners for the last two slots at the end-of-season Masters Cup.
World number one Roger Federer breezed through to the Halle Open semi-finals with a 6-3, 6-4 win over Germany's Philipp Kohlschreiber.
But fellow Argentines Gaston Gaudio and the indefatigable Guillermo Coria won in straight sets as did Russian Marat Safin
The world No.1 shrugged off sweltering conditions beat Olivier Rochus in the second round of the Nasdaq-100 Open.
World number one and defending champion Roger Federer won an epic 20-18 tie-break to seal a 6-3, 7-6 win over Marat Safin and place in the Masters Cup final.
Unheralded Igor Kunitsyn upset former world number one Marat Safin 7-6, 6-7, 6-3 in an all-Russian Kremlin Cup final to clinch his maiden title.
World number one Roger Federer will meet second seed Andy Roddick in the final of the Thailand Open after both claimed three-set victories.
Marat Safin and Mikhail won the doubles to give Russia a 3-0 lead in their Davis Cup World Group playoff tie.
World number one Justine Henin was dumped out of the German Open on Thursday, losing 5-7, 6-3, 6-1 to 13th seed Dinara Safina of Russia in the third round.
Kim Clijsters beat Dinara Safina, while Mary Pierce downed Tatiana Golovin in the semi-final of the Paris Open.
Spain's Feliciano Lopez sent the Australian ninth seed spinning out of the Madrid Masters on a night of surprises.
Second seed Tommy Haas and No 3 Marat Safin were ousted from the Washington Open.
In the other semi-final at the San Jose Open, German sixth seed Benjamin Becker, who upset Marat Safin will take on Ivo Karlovic.
The American was beaten by world number 103 Ivo Karlovic of Croatia in the second round.
The Argentine No 1 overpowered Russia's Marat Safin in the second singles after Nikolay Davydenko beat Juan Ignacio Chela.
Bob and Mike Bryan beat Mikhail Youzhny and Dmitry Tursunov in the doubles to enable the United States pull back 1-2 in their Davis Cup semi-final against Russia.
Carlos Moya is fit, in form and utterly convinced he is now a better all-round player than when he won the French Open as a fearless 21-year-old back in 1998
'Of course I am happy to reach No. 1. It was my goal since I was young and especially my goal in the latest times.'
The Russian ace will meet defending champion Andre Agassi in the semi-finals of the Australian Open. A round-up of Tuesday's matches.\n\n
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