Rhodium-Catalyzed Asymmetric Hydrogenation of Functionalized Olefins Using Monodentate Spiro Phosphoramidite Ligands

Fu, Yu; Guo, Xun‐Xiang; Zhu, Shou‐Fei; Hu, Aiguo; Xie, Jian‐Hua; Zhou, Qi‐Lin

doi:10.1021/jo049655z

Cited by 84 publications

(43 citation statements)

References 65 publications

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“…Zhou and co-workers [147] reported a highly enantioselective hydrogenation using Rh complexes of the siphos ligand (164) [Eq. (51); cod = cyclooctadiene].…”

Section: Reviewsmentioning

confidence: 99%

“…[147] Only one ligand was suggested to be bonded to the rhodium center in the active catalyst (ML model). [147] However, this is unlikely in view of the mechanistic studies of Reetz, Blackmond, et al [145] A strong (+)-NLE was observed in the asymmetric hydrogenation of ethyl acetoacetate promoted by [(binap)-Ru(Br) 2 ] prepared in situ from scalemic (S)-binap [165; Eq. (52)].…”

Section: Reviewsmentioning

confidence: 99%

See 1 more Smart Citation

Nonlinear Effects in Asymmetric Catalysis

Satyanarayana¹,

Abraham²,

Kagan³

2008

Angew Chem Int Ed

500

273

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There is a need for the preparation of enantiomerically pure compounds for various applications. An efficient approach to achieve this goal is asymmetric catalysis. The chiral catalyst is usually prepared from a chiral auxiliary, which itself is derived from a natural product or by resolution of a racemic precursor. The use of non-enantiopure chiral auxiliaries in asymmetric catalysis seems unattractive to preparative chemists, since the anticipated enantiomeric excess (ee) of the reaction product should be proportional to the ee value of the chiral auxiliary (linearity). In fact, some deviation from linearity may arise. Such nonlinear effects can be rich in mechanistic information and can be synthetically useful (asymmetric amplification). This Review documents the advances made during the last decade in the use of nonlinear effects in the area of organometallic and organic catalysis.

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“…Zhou and co-workers [147] reported a highly enantioselective hydrogenation using Rh complexes of the siphos ligand (164) [Eq. (51); cod = cyclooctadiene].…”

Section: Reviewsmentioning

confidence: 99%

Section: Reviewsmentioning

confidence: 99%

Nonlinear Effects in Asymmetric Catalysis

Satyanarayana¹,

Abraham²,

Kagan³

2008

Angew Chem Int Ed

500

273

View full text Add to dashboard Cite

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“…60 Some recently developed monodentate axial chiral P-ligands induced remarkably high enantioselectivities in the Rhcatalyzed enantioselective alkene hydrogenation, even comparable with those obtained using the best bidentate phosphines. 61 Monophosphines with axial chirality, e.g., MOP -(2 0 -methoxy-1,1 0 -binaphthyl-2-yl)diphenylphosphine family ligands, 62 and other monodentate binaphthyl-based ligands, as well as diaryl-63 and diheteroaryl-backbone ligands, or similar to them monodentate phosphorus ligands with a spiro scaffold [64][65][66] are widely used for transitionmetal-catalyzed asymmetric C À ÀC bond hydrogenation. [67][68][69] Selected examples of those types of ligands are shown in Figure 29.4.…”

Section: Diaryl-based Monodentate Ligands With Axialmentioning

confidence: 99%

Stereoselective Hydrogenation ofCCBonds: Application to Drug and Natural Product Synthesis

Andrushko

2013

Stereoselective Synthesis of Drugs and Natural Products

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Asymmetric homogeneous hydrogenation is perhaps one of the most researched areas in homogeneous catalysis; thus, it is now used in numerous innovative applications in stereoselective syntheses of many chiral pharmaceutical and natural products. Metal complexes, derived from transition metals, like Rh, Ru, Ir, and so on, and chiral ligands (usually mono‐ or diphosphine ligands), are widely used as catalysts in asymmetric alkene hydrogenation as a result of their efficiency in the preparation of enantiopure compounds with excellent atom economy. This chapter provides many interesting examples of homogeneous enantio‐ and diastereoselective hydrogenation of CC bonds, highlighting the utility of these methods as useful synthetic tools for the construction of stereogenic centers in stereoselective drug and natural product syntheses.

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“…The rhodium complex containing a SIPHOS ligand 1a is also an efficient catalyst for the asymmetric hydrogenation of cyclic enamides (Scheme 8.5). Under the conditions of 100 bar H 2 at 0 C in toluene, N-(1,2-dehydro-1-indanyl)acetamides 11a-11c were hydrogenated to the corresponding cyclic amines 12a-12c with 94, 88, and 95% ee, respectively [23].…”

Section: Asymmetric Hydrogenation Of Enamidesmentioning

confidence: 99%

Enantioselective Hydrogenation of Enamines with Monodentate Phosphorus Ligands

Zhou

Xie

2010

Chiral Amine Synthesis

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Chiral amines are widely used as chiral ligands, auxiliaries, resolving agents, and important intermediates in synthetic chemistry. Asymmetric hydrogenation of enamines such as enamides is an atom economic and straightforward protocol for the preparation of chiral amines. In 1972, Kagan reported the first example of asymmetric hydrogenation of enamides with chiral Rh-DIOP complex as a catalyst [1]. This opened a new window for the asymmetric synthesis of chiral N-acyl amines although the enantioselectivity of the reaction was not more than 78% ee (Scheme 8.1). When Noyori et al. introduced chiral Ru-BINAP, it significantly increased the level of enantioselectivity to 99.5% ee in the asymmetric hydrogenation of N-acyl-1-alkylidenetetrahydroisoquinolines [2]. However, this ruthenium-catalyzed asymmetric hydrogenation is very sensitive to the stereochemistry of the enamide, with only the (Z)-isomer of the enamide being hydrogenated while the (E)-isomer was recovered intact (Scheme 8.2). Another breakthrough in this field came in 1996 when Burk et al. showed that chiral rhodium complexes bearing a diphosphine ligand Me-DuPHOS or Me-BPE could hydrogenate a-arylenamides to yield a wide variety of valuable a-1-arylethylamine derivatives with high enantioselectivities (up to 98.5% ee) (Scheme 8.3) [3]. The merit of this hydrogenation is that both (E)-and (Z)-isomers of b-substituted enamides can be hydrogenated, thus enlarging the substrate scope of the reaction. Subsequently, many efficient diphosphines, such as BICP (bis(diphenylphosphino)dicyclopentane) [4], PennPhosP, NHAc NHAc 1 bar H 2 [RhCl(COD) 2 ] 2 /(S,S)-DIOP EtOH-C 6 H 6 (2 :1), rt 95% yield, 78% ee PPh 2 PPh 2 O O (S,S)-DIOP Scheme 8.1 Rh-DIOP catalyzed asymmetric hydrogenation of enamides.

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Rhodium-Catalyzed Asymmetric Hydrogenation of Functionalized Olefins Using Monodentate Spiro Phosphoramidite Ligands

Cited by 84 publications

References 65 publications

Nonlinear Effects in Asymmetric Catalysis

Nonlinear Effects in Asymmetric Catalysis

Stereoselective Hydrogenation ofCCBonds: Application to Drug and Natural Product Synthesis

Enantioselective Hydrogenation of Enamines with Monodentate Phosphorus Ligands

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