In the men's event, world number one Roger Federer was drawn against Russian Nikolay Davydenko.
Rafael Nadal, Robin Soderling, Novak Djokovic and Nikolay Davydenko kick off Group B on Monday.
The No. 6 seed Jo-Wilfried Tsonga, from France, triumphed 7-6 6-2 over Russia's Nikolay Davydenko.
Davydenko, who beat Nadal in the final last year, was surprised by his lack of stamina.
That was enough to end Soderling's resistence as Davydenko held serve twice to go through.
"He (Davydenko) played very well the last couple of times we've played, " said Federer.
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U.S. hopes were boosted by a superb win by 23rd seed Mardy Fish over Russian Nikolay Davydenko.
But the Briton faces a difficult second-round tie in Paris as he comes up against third seed Davydenko.
At 4-4 in the breaker, Soderling tamely netted to hand Davydenko the chance he had been waiting for.
Davydenko refused to be discouraged by that setback and broke for a 4-2 lead in the deciding set.
"I wanted to build up confidence before Roland Garros so I'm pleased I've done so well here, " said Davydenko.
Earlier, Russia's Nikolay Davydenko raced into the final after a comfortable 7-5 6-1 win over unseeded Martin Verkerk .
Paradorn Srichaphan showed flashes of his form of old as he upset sixth seed Nikolay Davydenko 6-4 7-5 6-3.
But Davydenko had recovered from his opening match defeat to Djokovic by crushing Nadal in straight sets on Wednesday.
Sixth seed Nikolay Davydenko was the first man to reach the third round, seeing off Igor Kunitsyn 6-4 6-2.
Murray's path to the title was made easier when the Croatian Marin Cilic stunned home favourite Davydenko 1-6 7-5 6-1.
Meanwhile, fourth seed Nikolay Davydenko pulled out of the tournament because of an elbow injury he struggled with in practice.
World No. 6 Nikolay Davydenko is the second seed, and the Russian's first match is against Feliciano Lopez of Spain.
Davydenko will play second seed Rafael Nadal in the final after the Spaniard earlier made short work of Viktor Troicki.
Fish battled back from two sets down to beat Davydenko 4-6 6-7 6-2 6-1 6-2 in three hours 26 minutes.
Fourth seed, Ivan Ljubicic , joined them when he lost a third set tie-break 11-9 to Russian Nikolay Davydenko .
The tournament, which is not an official ATP Tour event, also featured Russia's Nikolay Davydenko and Federer's Swiss compatriot Stanislas Wawrinka.
The Gold Group features Rafael Nadal, Nikolay Davydenko, Tommy Robredo and James Blake, all of whom begin their campaign on Monday.
Davydenko then called for the doctor at the changeover but showed no sign of discomfort when he returned to the court.
Federer's win sets up an intriguing encounter against Davydenko, who has beaten the world number one in their previous two encounters.
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Russia have named Marat Safin in their squad, despite his wrist injury, along with Yevgeny Kafelnikov, Mikhail Youzhny and Nikolay Davydenko.
Meanwhile, Federer said he was looking forward to the showdown against Davydenko.
"When I played him last year he had good form, " Davydenko said.
In other ATP action Saturday, France's Richard Gasquet beat Nikolay Davydenko of Russia 3-6 7-6 6-3 to win the Qatar Open title.
Davydenko remained ahead of Fernando Verdasco in the race to secure the two remaining places for the eight-man showpiece event later this month.
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