Diversity-Oriented Approach to 1,2,3,4-Tetrahydroisoquinoline-3-carboxylic Acid (Tic) Derivatives Using Diethyl Acetamidomalonate as a Glycine Equivalent: Further Expansion by Suzuki–Miyaura Cross-Coupling Reaction

Diversity Oriented Approach to Polycyclic Compounds through the Diels–Alder Reaction and the Suzuki Coupling

“…(2) use of a variety of dienophiles during the DA step (D 2 ); (3) thermal rearrangement of sultine 13 to give the corresponding sulfone and subsequent alkylation of the sulfone moiety with electrophiles containing a terminally unsaturated tether, followed by intramolecular DA reaction [20] (D 3 ); (4) use different gylcine equivalents [21] to prepare αamino acid derivatives (D 4 , D 8 , and D 10 ); (5) during the hydrolysis of isocyanide derivative, diverse protecting groups [17d] can be introduced into the α-amino acid moiety (D 9 ); (6) with the availability of more than a thousand commercially available boronic acids, the SM cross-coupling step can be used to functionalize the Tic derivatives [22] and other unusual α-amino acid derivatives (indan and tetralinbased α-amino acid derivatives) (D 5 ); (7) the substituents present in the boronic acid can be used as an additional handle for further synthetic manipulation (D 6 ); (8) oxidative coupling [23] of the SM products can generate carbonrich [24] Tic derivatives (D 7 ).…”

Development of New Synthetic Strategies, Tactics and their Applications

“…[8b] In addition, in 2010, we have envisioned a new protocol toward the synthesis of Tic derivatives by employing alkylation and SM reaction as key steps (Scheme 99). [126] In 2011, we have reported 1,2,3,4-tetrahydro-β-carboline (THBC) derivatives using diethyl acetamidomalonate (DEAM, 320) starting with dibromo indole derivatives such as 324 and 325. Here, the DEAM has been employed as a useful glycine equivalent (Scheme 100).…”

“…In connection with our “building block approach”, we have shown that cyclotrimerization strategy is useful for their preparation . In addition, in 2010, we have envisioned a new protocol toward the synthesis of Tic derivatives by employing alkylation and SM reaction as key steps (Scheme ) …”

Diversity-Oriented Approaches to Unusual α-Amino Acids and Peptides: Step Economy, Atom Economy, Redox Economy, and Beyond

“…For example, compound 39 was reacted with DEAM in the presence of K 2 CO 3 under PTC conditions to generate Tic derivative 40a, which undergoes a Suzuki−Miyaura (SM) cross-coupling reaction with various boronic acids to deliver different Tic derivatives 41a−d (Scheme 10). 23 This methodology was also extended to synthesize carbocyclic ring fused Tic (40b,c), heterocyclic Tic derivative (40d), cyclophane-based Tic derivative (40e), and higher analogues of Tic (Sic and Hic, 40f,g) by reacting the corresponding dibromo compound with DEAM. Furthermore, this methodology was used to obtain the indole-based Tic 40h (tetrahydro-β-carboline) derivative.…”

“…In this regard, alkylation of DEAM with a suitable 1,2-bis(bromomethyl)-4,5-diiodobenzene or 4,5-diiodo-α,α′-dibromo- o -xylene ( 39 ) has been used to generate various Tic derivatives. For example, compound 39 was reacted with DEAM in the presence of K 2 CO 3 under PTC conditions to generate Tic derivative 40a , which undergoes a Suzuki–Miyaura (SM) cross-coupling reaction with various boronic acids to deliver different Tic derivatives 41a – d (Scheme ) . This methodology was also extended to synthesize carbocyclic ring fused Tic ( 40b , c ), heterocyclic Tic derivative ( 40d ), cyclophane-based Tic derivative ( 40e ), and higher analogues of Tic (Sic and Hic, 40f , g ) by reacting the corresponding dibromo compound with DEAM.…”