The main pairing was going to be Jack and Kate. They would become the group's leaders. Jack would be the analytical leader and Kate would be the practical leader. This would lend support for balance if the group was going to create a new community on the island. Under the guide plan, Charlie would be accused of murder, and Kate would defend him. Jack, in the mean time, would probably treat Charlie for his withdrawal symptoms and therefore back Kate in the island trial. As a result, Charlie was supposed to become Jack's assistant. At the same time, Locke would be an adversary against the Kate-Jack leadership group.
The next major pair would have been the Sawyer and Shannon relationship. There pairing would be the show's first island hook-up. Shannon has a lazy golddigger's spirit, and Sawyer was the hoarder of material goods so he fit her profile. Boone, her brother, would always be her protector, so much so that he would be at odds with Sawyer. In the guide, the two have a vicious fight but don't allow the group in on the reason for their dispute. Later on, they have to work together to rescue Shannon from kidnappers.
The third major pairing was going to be with Sun and Michael. Sun was to have a more assertive and active role in the camp, as an alternative medicine healer. She was to be Claire's nurse maid during Claire's pregnancy. Since Sun was estranged from her husband Jin, there was supposed to be a long flirtation between Michael and Sun. Jin would be jealous of this, but had no means to communicate his anger. So he has to forge an alliance with Walt in order to learn English. It is not mentioned, but it is possible, that if the back story of Sun and Jin contained the infertility issue, then it would make some sense that Sun would gravitate toward Michael, a single parent, in order to form a family bond with him and his son. Likewise, Jin could also have the same feeling about having a family, and he could gravitate toward Claire and her new baby. Such as rotation of bonds and emotions could lead to several story lines on how each of them would cope with their new suitors and situations.
Though not put together in the guide as a team, it would seem that Hurley and Sayid would become good friends because each of them were practical problem solvers. The guide had Hurley's character being an international repo-man who could charm the collateral from debtors. Sayid was supposed to be an independent man who fled his country on a mission to find his true love. It would seem that these two characters would work well together as mediators between the group's potential factions.
It could be said that the original guide's character relationship road map was better plotted out that what actually happened in the series.
