Ortho-TMS benzaldehyde, an effective bifunctional linchpin for Type II Anion Relay Chemistry (ARC), permits efficient multi-component union of a variety of nucleophiles and electrophiles, including the first example of a Pd-mediated ARC Type II process. To demonstrate the utility of the Type II ARC protocol, a "proof of concept" synthetic sequence was designed and implemented for construction of a focused library of "natural product-like" compounds. Nature, with beautiful elegance, constructs natural products often in iterative fashion with both superb efficiency and exquisite stereochemical control.[1] For more than 100 years chemists have atempted to mimic the elegance of Nature with laboratory syntheses. The shortcomings of many synthetic ventures however lie in the multi-step sequences, often leading to minimum structure augmentation, in conjunction with isolation and purification at each stage, leading to inefficient material advancement. Fortunately, multi-component reactions[2] hold considerable promise of alleviating this inefficiency by orchestrating the conversion of simple starting materials, in a single (one-pot) operation, to advanced intermediates of high structural complexity without the need for multiple isolations and purifications.[3] Towards this end, we recently turned to the development of multi-component reaction sequences exploiting Anion Relay Chemistry (ARC).[4] At the highest level, the ARC tactic can be divided into two processes involving anion migration either through bonds or though space, the latter requiring the availability of a carrier to transport the negative charge. A simple example of "through-bond" anion relay is the well-known conjugate addition, through the π-system, with subsequent capture of the intermediate enolate. For "through-space" anion relay two possibilities exist involving σ-bonds (Type I and II), the difference residing in the resulting locus of the transposed anion. Type I ARC is defined as a multi-component coupling protocol (Scheme 1), wherein a linchpin nucleophile reacts with an electrophile to generate an oxyanion that subsequently transfers (i.e., relays) the negative charge "back" to the initiating site, followed by reaction with a suitable electrophile. The Type II process, entails reaction of a nucleophile with a bifunctional electrophilic linchpin to generate an anionic species that relays the negative charge to a new (i.e., different) locus, which then reacts with a second electrophile. An important feature of the Type II ARC process is the potential for iteration with a sequential series of bifunctional linchpins, a process not disimilar to living polymerization. [5] In 1997, based on the early work of Matsuda,[6] Tietze,[7] and Oshima,[8] we introduced an example of the Type I ARC process involving mono-silyl dithianes,[9] which through aegis of a solvent-controlled Brook rearrangement[10] led to the development of an effective three-component union protocol employing a wide variety of different second electrophiles. The utility of this process w...