Enantioselective syntheses of indanes: from organocatalysis to C–H functionalization

Abstract

The indanyl core is ubiquitous in a large variety of drugs and natural products. Importantly, the ever-increasing demand for chiral catalysts bearing this scaffold calls for state of the art methods allowing for a step-economical enantioselective access to this structural motif. We herein summarize the asymmetric syntheses of indanes with a particular focus on asymmetric catalysis, covering the literature of the last decade until July 2015.

Carbene‐Catalyzed Desymmetrization and Direct Construction of Arenes with All‐Carbon Quaternary Chiral Center

“…[4] Among the molecules containing arenes with chiral centers,i ndane derivatives having an all-carbon quaternary chiral center ( Figure 1a)a re particularly difficult to make in optically enriched forms. [5] Forexample,the natural product coprinastatin epimer [6] and preclinical drug [7] MK-3207 are available only in ar acemic form by current synthetic methods (Figure 1a). Theu se of chiral chromatography is required to obtain the enantiomerically enriched isomer.…”

A new route towards dithienoquinazoline and benzo[f]thieno[3,2-h]quinazoline systems using Pd-catalyzed intramolecular cyclization under microwave irradiation

“…Thus, incomplete conversion of the starting reagents 3 and 4 into target products 5 was observed even after long reaction times (up to 2 weeks). In all cases, the starting reagent 3a-g was partially recovered after the reaction was stopped (see Table 1, entries [8][9][10][11][12][13][14][15]. Mercury 25 representation of the X-ray crystal structure of 5a with thermal ellipsoids of 50% probability.…”

“…[6][7][8][9][10] Palladium-catalyzed C-H intermolecular and/or intramolecular arylation offers one of the most efficient and reliable methods for the construction of different polycyclic structures. [11][12][13][14][15] In this communication, we present a new and simple route to dithienoquinazoline and benzo [f]thieno [3,2-h]quinazoline systems I-III, based on Pd-catalyzed intramolecular cyclization, proceeding under microwave irradiation.…”

Carbene‐Catalyzed Desymmetrization and Direct Construction of Arenes with All‐Carbon Quaternary Chiral Center

“…[3] However,w hen chiral centers (particularly all-carbon quaternary centers) are present in the neighboring regions of the arenes,t he synthetic tasks become very challenging.There are few effective approaches available for construction of substituted benzenes with simultaneous installation of chiral centers. [5] Forexample,the natural product coprinastatin epimer [6] and preclinical drug [7] MK-3207 are available only in ar acemic form by current synthetic methods (Figure 1a). [5] Forexample,the natural product coprinastatin epimer [6] and preclinical drug [7] MK-3207 are available only in ar acemic form by current synthetic methods (Figure 1a).…”