Asymmetric syntheses. 20. Enantioselective hydrosilylation of ketones with [Rh(cod)Cl]2/thiazolidine catalysts

Brunner, Henri; Becker, Richard; Riepl, Georg

doi:10.1021/om00087a006

Cited by 139 publications

(20 citation statements)

References 7 publications

(10 reference statements)

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“…Chiral rhodium catalysts often use bidendate P,P, P,N or N,N ligands, such as PYTHIA, [10] PYBOX [11] or HETPHOX. [12] High enantioselectivities (over 90% ee) for the standard AHS of acetophenone were achieved with chiral diphosphine [13] or pyridine-phosphine [14] ligands having a ferrocene structural unit, as well as with a chiral P,S ligand reported by Evans.…”

Section: Introductionmentioning

confidence: 99%

Convenient Enantioselective Hydrosilylation of Ketones Catalyzed by Zinc‐Macrocyclic Oligoamine Complexes

2009

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Chiral macrocyclic tetra-and hexamine macrocycles derived from trans-1,2-diaminocyclohexane (DACH) in complexes with diethylzinc efficiently catalyze the asymmetric hydrosilylation of aryl alkyl ketones with enantiomeric excess of the product up to 89%. The cyclic structure of the trianglamine ligand increases the enantioselectivity of the reaction, in comparison to the catalysis with the acyclic N,N'-dibenzyl-DACH ligand. Density functional theory (DFT) computations on the structures of ligand-zinc complexes and on the structures of these complexes with a coordinated acetophenone molecule allow us to rationalize the direction of the asymmetric induction of the hydrosilylation reaction as well as the superiority of the cyclic ligand compared to the acyclic one. This is the first example of asymmetric catalysis for the hydrosilylation reaction of ketones with the use of a readily available, inexpensive, and reusable macrocyclic trianglamine ligand.

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Section: Introductionmentioning

confidence: 99%

Convenient Enantioselective Hydrosilylation of Ketones Catalyzed by Zinc‐Macrocyclic Oligoamine Complexes

2009

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“…This has been explained as resulting from different characteristics, namely, significantly different rates of reaction of the two diastereoisomeric catalysts or lack of coordination of one of the diastereoisomers. 21,36,37…”

Section: Scheme 2mentioning

confidence: 99%

d-Penicillamine and l-cysteine derived thiazolidine catalysts: an efficient approach to both enantiomers of secondary alcohols

et al. 2016

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D-Penicillamine derived thiazolidine ligands were prepared in a two-step synthetic sequence and used in the enantioselective alkylation of a variety of aromatic aldehydes with diethylzinc at room temperature. Excellent ee, up to >99%, and nearly complete conversions were observed. Structurally analogous L-cysteine derived thiazolidine ligands were also synthesized and tested for comparative purposes, resulting in very good, albeit slightly lower selectivities, up to 89%. The combined use of these two types of thiazolidines constitutes a very interesting strategy for synthesizing both (S) and (R) enantiomers of chiral secondary alcohols, thus leading the way to a myriad of useful optically active products with opposite absolute configurations.

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“…For background to compounds containing thiazoline or thiazolidine rings, see: Bolos et al (2002); Pontiki et al (2006); Shih & Ke (2004). For related structures, see: Brunner et al (1984Brunner et al ( , 2001). For the preparation of d-penicillamine-coordinated metal complexes, see: Igashira-Kamiyama & Konno (2011).…”

Section: Related Literaturementioning

confidence: 99%

Crystal structure of (2S,4S)-5,5-dimethyl-2-(pyridin-2-yl)-1,3-thiazolidine-4-carboxylic acid

et al. 2014

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In the title compound, C11H14N2O2S, the thiazolidine ring has an envelope conformation with the C atom bonded to the carboxylic acid group at the flap. Two C atoms of the thiazolidine ring adopt S conformations. In the crystal, O—H⋯N hydrogen bonds between the amine and carboxylic acid groups construct a helical chain structure along the a-axis direction. The chains are further connected via weak C—H⋯π contacts, forming a layer parallel to the ac plane.

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Asymmetric syntheses. 20. Enantioselective hydrosilylation of ketones with [Rh(cod)Cl]2/thiazolidine catalysts

Cited by 139 publications

References 7 publications

Convenient Enantioselective Hydrosilylation of Ketones Catalyzed by Zinc‐Macrocyclic Oligoamine Complexes

Convenient Enantioselective Hydrosilylation of Ketones Catalyzed by Zinc‐Macrocyclic Oligoamine Complexes

d-Penicillamine and l-cysteine derived thiazolidine catalysts: an efficient approach to both enantiomers of secondary alcohols

Crystal structure of (2S,4S)-5,5-dimethyl-2-(pyridin-2-yl)-1,3-thiazolidine-4-carboxylic acid

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