If I understand this correctly, you connect to the iSCSI share from within the guest OS.
In that case, vSphere will have no knowledge of that connection.
You can use the Get-WMI cmdlet inside the guest OS to retrieve iSCSI information from the MSiSCSI_PortalInfoClass for example.
If you are using the MS iSCSI Target v3.3 inside your guest OS, you can use the cmdlets that come with iSCSI.
You can launch such a PowerShell script inside your guest OS with the Invoke-VMScript cmdlet.