The cross-coupling reaction was first validated with N-methyl-substituted iodo-aminoalcohol 1a, readily synthesized from (Z)-(3-bromo-2-iodo-prop-1-enyl)benzene and N-methylethanolamine. Stoltz had reported the formation of the corresponding enol ether 2a in 86% yield after 24 h; 31b in our hands, full consumption of starting material was observed in less than 30 min and enol ether 2a was isolated in 76% yield. Iodo-aminoalcohol 1b reacted similarly, affording N-benzyl-protected enol ether 2b in excellent yield. While benzylamines can be deprotected to provide the corresponding secondary amine, carbamates and sulfonamides are more commonly used amine protecting groups and were more attractive for our purposes. Unfortunately, both Boc-protected aminoalcohol 1c and tosyl analogue 1d failed to react; neither substrate showed any conversion after 24 h at room temperature nor after heating the reaction mixtures for an additional 24 h at 60 °C. We therefore targeted secondary amine 1e directly. While the reaction time proved variable (1.5-24 h), cyclization afforded enol ether 2e, consistently in around 60% yield. Subsequent protection of the embedded secondary amine as its Boc carbamate 2c and tosyl sulfonamide 2d proceeded without event. Thus, while we were unable to extend Stoltz's cross-coupling methodology to substrates containing more electron-withdrawing carbamates and sulfonamides, 34 the successful application of a secondary amine substrate, which allows post-coupling derivatization, usefully extends the scope of this methodology. Finally, we explored the synthesis of our target molecule, namely 1,1-disubstituted enol ether 2f. Stoltz had reported its formation from iodoalcohol 1f in 40% yield; Scheme 2. Synthesis of bis-morpholine spiroacetal 8 however, we were only able to achieve 20% conversion at best. We therefore turned to a different route that ultimately provided a higher yielding, more practical and scalable synthesis of this enol ether. We envisaged enol ether 2f could alternatively be accessed via dehydrohalogenation 36 of the corresponding 2-halomethylsubstituted morpholine. Attempted iodoetherification 37,38 of 2-(allyl(benzyl)amino)ethanol either led to various unidentified side-products or extensive decomposition. Instead, 2-chloromethylmorpholine 3 was prepared in a two-step, one-pot operation, first introduced by Loftus 39a and later improved by Matsumoto and co-workers: 39b treatment of N-benzylethanolamine ( ) with an equimolar quantity of epichlorohydrin (5) in the absence of solvent at room temperature, followed by the addition of 98% H2SO4 and heating at 170 °C, afforded 2-chloromethylmorpholine 3 in 87% yield (Scheme 2). While this reaction sequence employs particularly harsh conditions in the second step, it proved remarkably scalable and was performed on 0.37 mol scale, providing 72 g of the target product.