Directed remote Metalation DreM

The mechanistic concept of CIPE, introduced in association with DoM reactions, is also utilized to rationalize metalations at remote positions relative to the DMG group or DreM. However, recent mechanistic studies have provided an in-depth comprehension of these transformations that extend beyond the scope of the CIPE model. 

DreM reactions can be classified into four categories (Fig. 26.8) [133]. Directed remote aromatic and lateral metalations on flexible biaryl structures bearing an electrophilic coordinating 

D Rigid reactant skeletons with coordinating DMG (e.g., CO2H) 

FIGURE 26.8 Directed remote metalation (DreM) categories. 

SCHEME 26.9 Mechanism of the DoM and DreM reactions of A/,iV-dialkylhiphenyl 2-carboxamides. 

---

Directed remote metalation (DreM) of biaryl amides and O-carbamates, conceptually based on the complex-induced proximity effect (CIPE) [15] provides, especially in view of their link to transition metal-catalyzed cross coupling regimens [16], general and versatile routes to fluorenones (16 —> 15, Scheme 4) [5,17] and biaryl amides (16 —> 17) [18] whose features are overriding Friedel-Crafts reactivity and yield enhancement in comparison to Suzuki-Miyaura coupling routes for highly hindered biaryls, respectively. Additional features of the O-carbamate DreM result is potential further DoM of 17 with appropriate phenol protection and cyclization to dibenzopyranones [18]. 

Directed remote Metalation (DreM) in aromatics and heteroaromatics ... 

Beyond Do M The Directed Remote Metalation (DreM) of Biaryl Amides and O-Carbamates I 351... 

Synthetic Methodology Derived from the DoM-Cross-Coupling Nexus 11097 14.3.2.1 Directed Remote Metallation (DreM) Connections... 

Scheme 14.17 Directed remote metallation (DreM) strategies to condensed aromatics and heteroaromatics.

Directed ortho and Remote Metalation (DoM and DreM) 106 Victor Snieckus and T. Macklin... 

For regioselective functionalizations of substituted arenes through directed ortho-metaUation reactions with stoichiometric amounts of organometaUic bases, see (a) Snieckus, V. and Macklin, T. (2005) Metallation of arenes. Directed ortho and remote metallation (DoM and DreM), in Handbook of C-H Transformations (ed. 

---