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While Large Language Models (LLMs) achieve state-of-the-art zero-shot extraction, enterprise deployment is hindered by compute costs and governance restricting Protected Health Information (PHI) from cloud APIs. We introduce SHIELD (Synthetic Human-annotated Identifier-replaced Entries for Learning and De-identification), a diverse dataset of 1,394 notes with 10,505 gold-standard PHI spans across 9 categories, built via set-cover diversity sampling with human-in-the-loop adjudication. We evaluate four LLMs (two proprietary, two open-weight) to establish a performance ceiling, then distill these capabilities into locally deployable Small Language Models (SLMs). 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