Rhodium(III)‐Catalyzed Intramolecular Hydroarylation, Amidoarylation, and Heck‐type Reaction: Three Distinct Pathways Determined by an Amide Directing Group

Abstract

Three different Rh(III)-catalyzed reaction pathways of a wide variety of tethered alkenes can be accessed through the change of the amide directing group. This provides an efficient route to a myriad of complex polycyclic products, many containing newly-formed all-carbon quaternary centers. Amidoarylations can highly diastereoselectively deliver products with up to three contiguous stereocenters.

Rhodium‐Catalyzed C(sp2)‐ or C(sp3)−H Bond Functionalization Assisted by Removable Directing Groups

“…[136] Depending on the type of N-substituent in the benzamide substrate,t he reaction proceeded by distinct pathways,l eading to either hydroarylation (106)o rd ehydrogenative Mizoroki-Heck-type products (see Section 6.2.4.2). [136] Depending on the type of N-substituent in the benzamide substrate,t he reaction proceeded by distinct pathways,l eading to either hydroarylation (106)o rd ehydrogenative Mizoroki-Heck-type products (see Section 6.2.4.2).…”

“…[136] An N-methoxyamide directing group is crucial to achieve the dehydrogenative Mizoroki-Heck-type product. [136] An N-methoxyamide directing group is crucial to achieve the dehydrogenative Mizoroki-Heck-type product.…”

Rh‐Catalyzed Synthesis of Oxygen‐Containing Heterocycles

“…They also developed enantioselective cyclization of aromatic imines with tethered 1,1-disubstituted alkenes through the combination of chiral phosphines and [RhCl(coe)] 2 [20]. A rhodium(III)-catalyzed distinct reaction pattern of tethered olefin-containing benzamides was developed by Rovis and coworkers (Scheme 6.11) [21]. This reaction might proceed through a seven-membered metallacycle 45, which could then undergo hydroarylation, β-H elimination, or amidoarylation, depending on the substituents on amides.…”

“…3,4-Dihydro-(1H)-benzopyranes were synthesized in excellent yields by Rovis through a Rh(III)-catalyzed intramolecular hydroarylation or amidoarylation (Scheme 6.30) [21]. …”

Iridium(I)‐Catalyzed Intramolecular Hydrocarbonation of Alkenes: Efficient Access to Cyclic Systems Bearing Quaternary Stereocenters

“…[4] Curiously,i ntramolecular versions of these reactions, which are highly attractive from as ynthetic point of view, have been far less studied. An alternative to generate this type of products consists of the use of Rh III or Ru II catalysts, [7] albeit these reactions are mechanistically different, requiring afinal protodemetalation. [5] Although significant progress has been achieved, most examples are limited to (hetero)aromatic precursors and usually proceed via endo-selective cyclizations [Scheme 1, Eq.…”