Systematic studies are presented demonstrating the complementarity of directed ortho metalation (DoM) and Ir-catalyzed strategies for the provision of borylated aromatics and their subsequent Suzuki–Miyaura coupling reactions. A new concept, the use of the TMS group, readily introduced by DoM, as a latent regiodirective moiety to overcome the otherwise problematic production of isomeric borylated product mixtures is presented. Additional electrophile-induced ipso-deborylation and DoM reactions of the Bpin products are described.

A general and efficient directed ortho metalation (DoM)-halogen dance (HD)-electrophile quench sequence for the synthesis of trisubstituted pyridyl O-carbamates is described. A second HD sequence furnishes highly functionalized tetrasubstituted pyridines. Furthermore, a hitherto unobserved double HD rearrangement is reported. Under similar LDA conditions, aromatic O-carbamates with OMe, Cl, and F substituents (4a-c) undergo either a HD-electrophile quench sequence, 4a-c --> 18-20, or a HD-anionic ortho Fries rearrangement, 4a-c --> 6a-c, respectively

Unexpected Smiles! An unusual and highly regioselective synthesis of dibenzoxazepinones by a domino sequence assisted by an unexpected Smiles rearrangement is reported. The process is effective on electronically differentiated phenols and shows a high tolerance to variation in the benzamide substituents. A plausible path for the reaction, supported by preliminary mechanistic data, is offered.

Strolling the ring: A general regioselective directed peri(C4)-metalation route to 1 through an in situ N-anionic protection of C2 is reported. The azaindoles may be elaborated by directed ortho metalation (DoM) and Suzuki coupling to more complex heterocyclic systems. An iterative ring-walk DoM sequence furnishes the exhaustively substituted 2. DMG=directed metalation group, TMEDA=N,N,N′,N′-tetramethylethylenediamine, TMS=trimethylsilyl.

A general synthesis of stable ortho-boropinacolato aryl and heteroaryl sulfonamides by directed ortho-metalation (DoM) and either MeOBPin or i-PrOBpin electrophile quench, 3 f 4, is described. A one-pot metalation␣Suzuki cross-coupling procedure for the synthesis of biaryls and heterobiaryls, 3 f 5, and a complementary DoM␣Ir-catalyzed boronation sequence (Scheme 6) are delineated.

Embodiments of the invention provide a method of using Schwartz Reagent, Cp2Zr(H)Cl, without accumulating or isolating it. Methods provide mixtures of Cp2ZrCl2, reductants that selectively reduce Cp2ZrCl2, and substrates. After reaction of Cp2ZrCl2 and the reductant, an intermediate reduction product is formed, apparently Schwartz Reagent. The in situ Schwartz Reagent then selectively reduces certain functional groups on the substrate. Substrates include tertiary amides, tertiary benzamides, aryl O-carbamates, and heteroaryl N-carbamates, which are reduced to aldehydes, benzaldehydes, aromatic alcohols, and heteroaromatics, respectively. Compared to prior methods, reagents are inexpensive and stable, reaction times are short, and reaction temperature in certain cases is conveniently room temperature. It has been estimated that using the in situ method described herein instead of synthesized or commercially obtained Schwartz Reagent provides a 50% reduction in cost