A Novel Three-Component Reaction Catalyzed by Dirhodium(II) Acetate:  Decomposition of Phenyldiazoacetate with Arylamine and Imine for Highly Diastereoselective Synthesis of 1,2-Diamines

Abstract

[reaction: see text] A practical highly diastereoselective synthesis of 1,2-diamines through carbon-carbon bond formation involving an ammonium ylide intermediate is reported for the first time. By treating methyl phenyldiazoacetate with arylamine and imine in the presence of dirhodium acetate, the erythro diastereomer of methyl 1,2-diaryl-1,2-diaminopropanoate is formed with stereochemical preferences greater than 10:1.

Modern Organic Synthesis with α-Diazocarbonyl Compounds

“…468 It was already known that catalyzed reaction of diazoacetate with imines led to aziridines via an iminium ylide intermediate. The addition of an arylamine to this combination produced a three-component reaction resulting in the formation of an ammonium ylide from arylamine and diazoacetate, followed by product formation through two competitive reaction pathways: (A) Chem.…”

Asymmetric Multicomponent Reactions Based on Trapping of Active Intermediates

“…The 3CR based on the trapping of ammonium ylide was a serendipity of a overlooked reaction during our investigation on the Rh(II)‐catalyzed aziridination of aryldiazoacetates with arylimines (path A, Scheme ) . When the impure imine 5 with unreacted para‐nitro aniline was used, an α,β‐bis(arylamino) ester 9 (path B), which incorporated the structural features of the diazo compound, the imine, and the aniline, was isolated (Scheme ). In this reaction, metal carbene reacted with concomitant aniline prior to imine to form ammonium ylide I , which was trapped by imine through intermediate 8 to obtain product 9 .…”

“…Based on the success of asymmetric reaction of oxonium ylides, we then studied the utilization of the combination of Rh 2 (OAc) 4 with a chiral BINOL‐derived phosphoric acid to induce an enantioselective three‐component Mannich‐type reaction of ammonium ylide. In previous investigation on the trapping of ammonium ylides with imine, this reaction had encountered several major restrictions: (1) only arylamines were effective in forming the active ylides for electrophilic trapping, (2) poor chemo‐ and/or diastereoselectivity were observed, and (3) no asymmetric version has been achieved. In current research, the combination of diazo compounds, carbamates 20 and imines was chosen as starting point for the 3CR employing the synergistic catalysis of Rh 2 (OAc) 4 and PPA (Scheme ).…”

Iron(III) Corroles and Porphyrins as Superior Catalysts for the Reactions of Diazoacetates with Nitrogen‐ or Sulfur‐Containing Nucleophilic Substrates: Synthetic Uses and Mechanistic Insights

“…Another attempt to obtain enantioselective reactions between aniline and EDP took advantage of the noncovalent conjugates formed between iron corrole 14 (Scheme 4) and serum albumins, a combination that has been successfully used for chiral induction in the sulfoxidation of thioanisoles by H 2 O 2 . [26] This approach led to high yields when performed at 25 8C in aqueous solutions with 0.1 mol % of 14 (Table 4, entries [11][12][13][14][15][16][17][18][19]. However, despite the milder reaction conditions, the use of five different albumins, and the various pH conditions applied, the alanine derivative was always obtained as a racemic mixture.…”

“…In this case, no reaction occurred even after 18 h. The most important outcome of this short investigation is that it readily explains the lack of chiral induction for the reaction of EDP when performed in the chiral environment provided by proteins (Scheme 4). Apparently, the lifetime of reaction intermediate Y (R = CH 3 in Scheme 5) is long enough (i.e., internal nitrogen-to- 18,19,27] There is also one report of a related case that involves iron porphyrin 3 b as the catalyst in a three-component reaction between aldehyde, phenyldiazomethane, and trimethyl phosphite. [28] In all of these investigations, the precursor of the ylide was proposed to be a metal-carbene formed by the interaction of the diazoalkane with the metal (B!C in Scheme 6).…”