PEOPLE’s most recent Sexiest Man Alive, Pierce Brosnan, 50, will act like James Bond, and Ozzy Osbourne, 53, will do his thing — that is, sing his heavy metal anthem “Paranoid” — when they appear before Queen Elizabeth, 76, and other members of the House of Windsor as part of the three-hour June 3 concert (“Party at the Palace”) to commemorate Her Majesty’s 50 years on the throne, PEOPLE has learned. Brosnan will introduce songstress Shirley Bassey, 65, who will deliver her signature song, “Goldfinger,” to the 12,000 invited attendees. As far as the running order of the great event is concerned, PEOPLE.com reports exclusively, Ricky Martin, 30, will be the first solo act of the night, doing “Living La Vida Loca.” Before the grand finale, which will be the Beatles’ “All You Need Is Love” (performed by Paul McCartney, among others), will be an American act: the Beach Boys’ Brian Wilson, 61, delivering “Good Vibrations” and “God Only Knows.” Ray Davies, 57, of The Kinks, may raise royal eyebrows with his song choice — his hit “Lola,” about a transvestite. Most of the acts plan to play one or two hits each. Insiders tell PEOPLE.com that, despite earlier hopes, Madonna, 43, now starring in a play in London’s West End, will not participate. However, taking part will be Steve Winwood, 54, who is set to lead the house band (which also has Phil Collins on drums) in “Keep on Running,” and Joe Cocker. Aretha Franklin and Elton John will pre-record their contributions. A source at the BBC — which is producing and broadcasting the show for worldwide distribution — told PEOPLE that Franklin, 60, tried to overcome her longtime fear of flying to attend the event, but she was unable to do so. Sir Elton, 55, has already taped his set at the palace. Blue will join Mis-teeq in a Motown medley. Other hosts include monologist Dame Edna Everage (also known as Barry Humphries, 68) and comedian Ben Elton, 43.