@article {25354,
	title = {Stereoselective Diels-Alder Reactions of gem-Diborylalkenes: Toward the Synthesis of gem-Diboron-Based Polymers},
	journal = {Journal of the American Chemical Society},
	volume = {143},
	number = {143},
	year = {2021},
	note = {Nadim Eghbarieh and Nicole Hanania contributed equally to the work.},
	pages = {6211-6220},
	abstract = {Although gem-diborylalkenes are known to be among the most valuable reagents in modern organic synthesis, providing a rapid access to a wide array of transformations, including the construction of C-C and C-heteroatom bonds, their use as dienophile-reactive groups has been rare. Herein we report the Diels-Alder (DA) reaction of (unsymmetrical) gem-diborylalkenes. These reactions provide a general and efficient method for the stereoselective conversion of gem-diborylalkenes to rapidly access 1,1-bisborylcyclohexenes. Using the same DA reaction manifold with borylated-dienes and gem-diborylalkenes, we also developed a concise, highly regioselective synthesis of 1,1,2-tris- and 1,1,3,4-tetrakis(boronates)cyclohexenes, a family of compounds that currently lack efficient synthetic access. Furthermore, DFT calculations provided insight into the underlying factors that control the chemo-, regio, and stereoselectivity of these DA reactions. This method also provides stereodivergent syntheses of gem-diboryl-norbornenes. The utility of the gem-diboryl-norbornene building blocks was demonstrated by ring-opening metathesis polymerization (ROMP), providing a highly modular approach to the first synthesis of the gem-diboron-based polymers. Additionally, these polymers have been successfully submitted to post-polymerization modification reactions. Given its simplicity and versatility, we believe that this novel DA and ROMP approach holds great promise for organoboron synthesis as well as organoboron-based polymers and that it will result in more novel transformations in both academic and industrial research.[[{"fid":"28219","view_mode":"default","type":"media","attributes":{"height":"404","width":"510","style":"float: left;","alt":"toc jacs","class":"media-element file-default"}}]]},
	url = {https://pubs.acs.org/doi/10.1021/jacs.1c01471},
	author = {Nadim Eghbarieh and Nicole Hanania and Alon Zamir and Molhm Nassir and Stein, Tamar and Ahmad Masarwa*}
}
