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No, he'll still be ineligible to adjust then because of the overstay:
https://www.uscis.gov/policy-manual/volume-7-part-b-chapter-3 "An alien is barred from adjustment of status if the alien is in an unlawful immigration status on the date of filing the adjustment application."
 
https://www.uscis.gov/policy-manual/volume-7-part-b-chapter-4
Any adjustment applicant is ineligible to adjust status under INA 245(a) if, other than through no fault of his or her own or for technical reasons, [1] he or she has ever:
Failed to continuously maintain a lawful status since entry into the United States; [2] or
Violated the terms of his or her nonimmigrant status.
 
And if he works without authorization that is yet another bar to adjustment: https://www.uscis.gov/policy-manual/volume-7-part-b-chapter-6
an alien is barred from adjusting status if:
He or she continues in or accepts unauthorized employment prior to filing an application for adjustment of status; [1] or
He or she has ever engaged in unauthorized employment, whether before or after filing an adjustment application. [2] 

Assuming he’s an adult sibling and not your legally dependent minor sibling, he can’t adjust status without an approved i130, and must be in legal status when that time comes... and yes it could take years anywhere from 5-25 years depending on if he ever gets married or not..
 
since he’s not able to apply for AOS and is not here currently on a work visa he’ll need to go home and apply for one based on his own skills and merits unless of course he is eligible for a different type of visa that permits his stay.. 
 
on the up side, he’ll still be able to come visit for holidays etc until his visa is approved
 
note, even if his petition becomes current he can’t just enter the country and apply for AOS that would be fraud 

You can file an I-130 for your brother.  It doesn't matter if he is single or married.  The current wait in the F4 category is 14 years for people born in Canada.  It's not 7 years.  Furthermore, USCIS approving the I-130 is only the first part.  Your brother would need to have a current Priority Date in the F4 category to be eligible for an immigration benefit through the petition you file for him, and the current wait is 14 years.  
 
He can not get a work permit based on the I-130 your file for him.  

He can not stay in the US based on the I-130 you file for him.
 
He can only adjust status based on the I-130 you file for him if his stay is legal in the US and his Priority Date is current.

There's no other options.