Highly Stereoselective Synthesis of Cyclopropylphosphonates Catalyzed by Chiral Ru(II)-Pheox Complex

Chanthamath, Soda; Ozaki, S.; Shibatomi, Kazutaka; Iwasa, Seiji

doi:10.1021/ol501135p

Cited by 34 publications

(12 citation statements)

References 26 publications

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“…The key reaction development was a Ru(II)‐Pheox‐catalyzed stereoselective cyclopropanation of olefins with diazomethyl‐phosphonates (Scheme 85). [174] This method was successfully applied to the preparation of optically active cyclopropyl‐phosphonate 243 in 78% yield and excellent diastereo‐ and enantioselectivity (99:1 dr, 99% ee). Reduction of the ester group with LiBH 4 gave the phosphonocyclopropanyl alcohol 244 in 86% yield with maintained excellent ee value.…”

Section: Asymmetric Construction Of Cyclopropane and Bicyclo‐[xyz]‐mentioning

confidence: 99%

Asymmetric Synthesis of Chiral Amino Carboxylic‐Phosphonic Acid Derivatives

Cahard

Cao

et al. 2020

Adv Synth Catal

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Chiral amino acids featuring a phosphonate pendant arm are an important type of biologically active scaffold. Here in this review, we comprehensively summarize the modern synthetic methods towards asymmetric construction of chiral amino carboxylic‐phosphonic acid derivatives. The main streams of such interesting compounds include phosphono‐containing α‐, β‐, and γ‐amino acid derivatives, amino acid fluorophosphonate derivatives, amino acid cyclopropanylphosphonate derivatives, and bisphosphono‐amino acid derivatives. Chiral resolution protocols, chiral auxiliary‐directed syntheses, and valorization of the pool of abundant chiral amino acid resources remain contemporary concerns, and meanwhile catalytic enantioselective synthesis has also emerged as a potent strategy as demonstrated by the latest advances.magnified image

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Section: Asymmetric Construction Of Cyclopropane and Bicyclo‐[xyz]‐mentioning

confidence: 99%

Asymmetric Synthesis of Chiral Amino Carboxylic‐Phosphonic Acid Derivatives

Cahard

Cao

et al. 2020

Adv Synth Catal

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“…In 2010, we developed a novel chiral complex, Ru(II)‐phenyloxazoline (Ru(II)‐Pheox) complex, which has a unique C 1 ‐symmetric structure (Figure ). Ru(II)‐Pheox can be easily synthesized from a commercially available benzoic acid derivative, an amino alcohol and a Ru source, and effectively promotes enantioselective intermolecular and intramolecular cyclopropanations with electron‐rich olefins, as well as electron‐deficient olefins, under mild reaction conditions.…”

Section: Introductionmentioning

confidence: 99%

Computational chemical analysis of Ru(II)‐Pheox–catalyzed highly enantioselective intramolecular cyclopropanation reactions

Nakagawa

Nakayama²,

Goto

et al. 2018

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Computational chemical analysis of Ru(II)‐Pheox–catalyzed highly enantioselective intramolecular cyclopropanation reactions was performed using density functional theory (DFT). In this study, cyclopropane ring–fused γ‐lactones, which are 5.8 kcal/mol more stable than the corresponding minor enantiomer, are obtained as the major product. The results of the calculations suggest that the enantioselectivity of the Ru(II)‐Pheox–catalyzed intramolecular cyclopropanation reaction is affected by the energy differences between the starting structures 5l and 5i. The reaction pathway was found to be a stepwise mechanism that proceeds through the formation of a metallacyclobutane intermediate. This is the first example of a computational chemical analysis of enantioselective control in an intramolecular carbene‐transfer reaction using C1‐symmetric catalysts.

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“… 211 − 213 The asymmetric cyclopropanation between diethyl diazomethylphosphonate ( 578 ) and a series of alkenes including styrene derivatives, α,β-unsaturated esters, ketones, and amides was carried out to provide the corresponding cyclopropylphosphonate products ( 579 ) in high yields and with excellent diastereoselectivity (up to 99:1 dr) and enantioselectivity (up to 97% ee ) ( Scheme 179 A). 211 Similarly, diazosulfones ( 580 ) reacted with various alkenes including vinyl ethers, vinyl amines, and vinyl carbamates to furnish chiral cyclopropyl sulfones ( 581 ) in high yields (up to 80%) with excellent trans -selectivity and enantioselectivity (up to 96% ee ) ( Scheme 179 B). 212 An asymmetric synthesis of various trifluoromethyl cyclopropanes ( 584 ) was achieved in high yields with excellent diastereoselectivity (up to 98:2 dr) and enantioselectivity (up to 96% ee ) by reacting in situ generated CF 3 CHN 2 ( 583b ) with a range of alkenes including vinyl ferrocene, vinyl ethers, vinyl amines, vinyl carbamates, and dienes ( Scheme 179 C).…”

Section: Mono(oxazoline) Ligandsmentioning

confidence: 99%

Further Developments and Applications of Oxazoline-Containing Ligands in Asymmetric Catalysis

et al. 2021

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The chiral oxazoline motif is present in many ligands that have been extensively applied in a series of important metal-catalyzed enantioselective reactions. This Review aims to provide a comprehensive overview of the most significant applications of oxazoline-containing ligands reported in the literature starting from 2009 until the end of 2018. The ligands are classified not by the reaction to which their metal complexes have been applied but by the nature of the denticity, chirality, and donor atoms involved. As a result, the continued development of ligand architectural design from mono(oxazolines), to bis(oxazolines), to tris(oxazolines) and tetra(oxazolines) and variations thereof can be more easily monitored by the reader. In addition, the key transition states of selected asymmetric transformations will be given to illustrate the features that give rise to high levels of asymmetric induction. As a further aid to the reader, we summarize the majority of schemes with representative examples that highlight the variation in % yields and % ee s for carefully selected substrates. This Review should be of particular interest to the experts in the field but also serve as a useful starting point to new researchers in this area. It is hoped that this Review will stimulate both the development/design of new ligands and their applications in novel metal-catalyzed asymmetric transformations.

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Highly Stereoselective Synthesis of Cyclopropylphosphonates Catalyzed by Chiral Ru(II)-Pheox Complex

Cited by 34 publications

References 26 publications

Asymmetric Synthesis of Chiral Amino Carboxylic‐Phosphonic Acid Derivatives

Asymmetric Synthesis of Chiral Amino Carboxylic‐Phosphonic Acid Derivatives

Computational chemical analysis of Ru(II)‐Pheox–catalyzed highly enantioselective intramolecular cyclopropanation reactions

Further Developments and Applications of Oxazoline-Containing Ligands in Asymmetric Catalysis

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