This is a bit of a long shot but have you tried booting with a floppy with the NTLDR and NTDETECT.com files on? It should then fail to find the Boot.ini file and default to loading from C:\Windows
The two files are in a ZIP on my website click here
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Synology invites you to visit them at Insomnia on 26th – 29th August. Book your tickets now and visit Synology.