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ABSTRACT: Carbenes and carbenoids are commonly employed for the synthesis of cyclopropane-containing compounds. Here we report the metal-free, intramolecular cyclopropanation of tethered alkenes by free carbenes derived from alkynes to construct structurally unique, multicyclic cyclopropanes with perfect atom economy. The nature of the tether influences both the rate of carbene formation as well as subsequent competing reaction events. Some of the substrates lead to metastable cyclopropane intermediates that further fragment to furnish interesting isomeric products by mechanistically novel processes. A removable siloxane tether can be utilized to achieve formal intermolecular cyclopropanations and to access cyclopropanol derivatives. 

Editor's Choice Featured Article https://pubs.acs.org/doi/full/10.1021/acs.joc.1c02590 

Frontline communities of California experience disproportionate social, economic, and environmental injustices, and climate change is exacerbating the root causes of inequity in those areas. Yet, climate adaptation and mitigation strategies often fail to meaningfully address the experience of frontline community stakeholders. Here, we present three challenges, three errors, and three solutions to better integrate frontline communities' needs in climate change research and to create more impactful policies. We base our perspective on our collective firsthand experiences and on scholarship to bridge local knowledge with hydroclimatic research and policymaking. Unawareness of local priorities (Challenge 1) is a consequence of Ignoring local knowledge (Error 1) that can be, in part, resolved with Information exchange and expansion of community-based participatory research (Solution 1). Unequal access to natural resources (Challenge 2) is often due to Top-down decision making (Error 2), but Buffer zones for environmental protection, green areas, air quality, and water security can help achieve environmental justice (Solution 2). Unequal access to public services (Challenge 3) is a historical issue that persists because of System abuse and tokenism (Error 3), and it may be partially resolved with Multi-benefit projects to create socioeconomic and environmental opportunities within frontline communities that include positive externalities for other stakeholders and public service improvements (Solution 3). The path forward in climate change policy decision-making must be grounded in collaboration with frontline community members and practitioners trained in working with vulnerable stakeholders. Addressing co-occurring inequities exacerbated by climate change requires transdisciplinary efforts to identify technical, policy, and engineering solutions.