Sigma Healthcare—which counts Australian billionaire brothers Jack and Sam Gance and their business partner Mario Verrochi as its biggest shareholders—is in talks to buy U.K. health and beauty retailer The Boots Group, doubling down on its expansion plans in London.

The potential sale of Boots in a deal that could be valued at over $10 billion to bidders including Sigma Healthcare and the Weston family, the controlling shareholder of Canada’s largest supermarket chain, Loblaw, was first reported by the Financial Times on Tuesday. A successful sale would........

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