Quaternary carbons can now be dissected into feedstock precursors, alkenes and carboxylic acids, via radical quaternization. Numerous high fraction sp 3 materials are now available in a fraction of the prior synthetic burden. Indeed, the approach outlined herein represents a complete departure from the mostly carbonyl-focused retrosynthetic analysis (Table ) historically utilized to forge such systems. In this simple protocol, two substrates classes converge into the same catalytic cycle in which an iron(III) catalyst undergoes reduction to iron(II) by either Zn or a silane/alkene combination, and oxidative capture by a redox-active ester returns the iron(III). Notably, the alkene cross-coupling involves iterative outer-sphere steps to form new C-C bonds using a single catalyst; the RAE cross-coupling exhibits perfect heteroselectivity. In contrast, inner sphere cross couplings that involve weak alkene-metal center complexes to form sp 3 -sp 3 linkages (e.g. Heck, Kulinkovich, 1,4-addition) often do not allow chemoselective merger of complex fragments. It has been widely recognized that fragment coupling simplifies retrosynthetic analysis by increasing convergency. Simple tools such as the reactions described herein point to a unique conceptual platform to decisively solve this vexing problem in organic synthesis. A sequence of FG/PG manupulations was inevitable due to the necessity of a carbonyl group to construct the 4º-carbon