Development of Dirhodium(II)-Catalyzed Generation and Enantioselective 1,3-Dipolar Cycloaddition of Carbonyl Ylides

Abstract

Catalytic, enantioselective, tandem carbonyl ylide formation/cycloaddition of 2-diazo-3,6-diketoester 2 with the use of dirhodium tetrakiscarboxylate and tetrakisbinaphtholphosphate catalysts to give the cycloadducts 3 in good yields and up to 90% ee is described.

Chiral Dirhodium Catalysts: A New Era for Asymmetric Catalysis

“…The main classes of these are detailed below. [27][28][29][30] reported the preparation of a new chiral dirhodium carboxylate complexes derived from Lproline (2)(3)(4)(5)(6)(7)(8)(9). The catalysts were prepared by ligand exchange in which the sodium salts of rhodium carbonates were exchanged with the appropriate N-substituted-sulphonyl-L-prolinate ligand (Fig.…”

“…The complex activity has been examined for asymmetric cyclopropanation of alkenes with vinyl and phenyl-diazoester giving a high enantioselectivities up to 92% [36]. In 2001, Hodgson et al [7] reported the preparation of two analogues of the McKervey and Betrilsson catalysts by applying the Callot method [35]. Again, the catalysts were fully characterized by NMR, Mass spectrometery, and CHNS analysis.…”

“…Ideally, a practical asymmetric catalyst is inexpensive and readily available in both enantiopure forms whilst providing high yields and enantioselectivities for a broad range of substrates in different reactions. A large number of complexes have been synthesized and many of these complexes have been studied and used in catalysis [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. The catalysis by dirhodium paddlewheel complexes has been an area of immense interest and extensive study over the past three decades -not only because most of the catalysts are highly stable to heat, moisture and ambient atmosphere but also for the asymmetric induction in the ylide generation [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19].…”

Chiral Dirhodium(II) Carboxylates: New Insights into the Effect of Ligand Stereo-Purity on Catalyst Structure and Enantioselectivity

“…Their remarkable selectivity has reached a stage where they can function as a powerful tool in building up value added molecules with complex structures [7,[15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34].…”

On the Structure of Chiral Dirhodium(II) Carboxylate Catalysts: Stereoselectivity Relevance and Insights

“…This immense interest originates from their exceptional ability to effectively catalyze a broad spectrum of reactions with high levels of chemo-, regio-and stereo-selectivity. These transformations involve aziridinations [16][17][18], C-H insertions [7,19,20], ylide transformations [21][22][23][24][25], Lewis acid-promoted reactions [21,[26][27][28][29][30], cross-coupling reactions [31], cyclopropanation and cyclopropenation reactions [32][33][34][35]. In fact, they have proven their potential, particularly, in the field of asymmetric synthesis.…”