Highly Chemoselective Catalytic Hydrogenation of Unsaturated Ketones and Aldehydes to Unsaturated Alcohols Using Phosphine-Stabilized Copper(I) Hydride Complexes

Chen, Jianxin; Daeuble, John F.; Brestensky, Donna M.; Stryker, Jeffrey M.

doi:10.1016/s0040-4020(99)01098-4

Cited by 146 publications

(86 citation statements)

References 37 publications

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“…This rate enhancement is likely due to greater solubility of the copper precatalyst in THF. An additional increase in rate was observed, as in previous systems (19,(32)(33)(34)(35)(36), when sterically hindered alcohols were added to the reaction mixture. Further, when reactions were performed under an atmosphere of air, the reaction rates were faster than those carried out under inert atmosphere (19,37).…”

Section: Resultssupporting

confidence: 82%

Copper-catalyzed asymmetric conjugate reduction as a route to novel β-azaheterocyclic acid derivatives

Rainka

Aye

Buchwald

2004

Proc. Natl. Acad. Sci. U.S.A.

104

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A chiral copper-hydride catalyst for the asymmetric conjugate reduction of ␣,␤-unsaturated carbonyl compounds has been used for the reduction of substrates containing ␤-nitrogen substituents. A new set of reaction conditions has allowed for a variety of ␤-azaheterocyclic acid derivatives to be synthesized in excellent yields and with high degrees of enantioselectivity. In addition, the effect that the nature of the nitrogen substituent has on the rate of the conjugate reduction reaction has been explored. Many ␤-amino acids and their derivatives are of interest as structural components and because of their biological activity (1-3). The asymmetric synthesis of these compounds has been realized through a variety of methods (1, 4, 5), most notably asymmetric Mannich reactions (6-8), diastereoselective or enantioselective conjugate additions (9-13), and the reduction of ␤-amido ␣,␤-unsaturated esters or nitriles (6,(14)(15)(16)(17)(18). Although the reduction of ␣,␤-unsaturated esters has proven to be a particularly powerful tool for this transformation, the various methods used are generally limited to substrates that contain a primary amido group in the ␤ position.We recently described a versatile system for the asymmetric conjugate reduction of a wide variety of ␣,␤-unsaturated carbonyl compounds (19)(20)(21)(22)(23)(24)(25)(26)(27). Appropriately substituted acyclic ␣,␤-unsaturated esters, cyclopentenones, lactones, and lactams could all be reduced in high yield and with excellent levels of enantioselectivity. However, to our knowledge there have been no successful conjugate reductions of substrates containing ␤-heteroatoms. One possible explanation for this is that deactivation of the enoate can occur by the interaction of a lone pair of electrons on the heteroatom with the conjugated system of the enoate. We therefore reasoned that suitable substrates for this reaction that contained ␤-heteroatoms would possess functional groups in which this interaction is minimized. We report here a method for the asymmetric conjugate reduction of ␣,␤-unsaturated carbonyl compounds substituted with a nitrogen in the ␤ position. This method allows for the preparation of a variety of azaheterocycles and derivatives not available by other methods of asymmetric reduction. MethodsPreparation of Substrates. Various ␤-iodo enoates were effectively coupled with azaheterocycles by using a modified protocol derived from our recently reported copper-catalyzed vinylation of amides and carbamates (Scheme 1) (28-31). For small quantities of material, an oven-dried Schlenk flask equipped with a Teflon-coated magnetic stir bar was allowed to cool to room temperature under nitrogen and then was charged with Cu(I) iodide (0.10 mmol), potassium phosphate (1.5 mmol), and (if a solid) the nitrogen nucleophile (1.5 mmol). The flask was then capped with a rubber septum, evacuated, and backfilled with nitrogen; this process was repeated one time. Toluene (0.50 ml) was added, followed by the diamine (0.20 mmol), the nitrogen nucleophile (if a liqui...

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Section: Resultssupporting

confidence: 82%

Copper-catalyzed asymmetric conjugate reduction as a route to novel β-azaheterocyclic acid derivatives

Rainka

Aye

Buchwald

2004

Proc. Natl. Acad. Sci. U.S.A.

104

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“…2-Methyl-1-phenyl-1-propanol (2ac). 19 Chlorophenyl)-1-propanol (2b). 21 1-(4-Bromophenyl)-1-propanol (2c).…”

Section: Methodsmentioning

confidence: 99%

Nickel-accelerated addition of dialkylzinc reagents to aldehydes. Application to enantioselective synthesis

Almansa¹,

Guijarro²,

Yus³

2006

Arkivoc

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The reaction of several dialkylzinc reagents with aromatic aldehydes 1 in the presence of a catalytic amount of nickel(II) acetylacetonate (5 mol%) at 0 ºC gave the expected addition products 2 in 1 h in very good yields. Aliphatic aldehydes 1 required stirring at room temperature for 24 h to afford the addition products in good yields. In comparison with non-catalyzed reactions this process represents a great improvement in reaction rate and selectivity for the formation of addition products. The enantioselective addition of diethylzinc to benzaldehyde 1a in the presence of the nickel catalyst and chiral aziridino alcohols 3 results in an interesting switch of the sense of the asymmetric induction in comparison with the nickel-free process.

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“…6,7,16,65,6 bility of compl 2-cyclohexen-5 equiv) to 3 ts), in C 6 D 6 r onding silyl en in small a oduct, 4c. 67 68 or the 1,4-conversion However, selectivity gly, in the m the stoivation has 69 and can of the copequilibrie presence drive the n, we also talyze 1,4-ns.…”

Section: Scheme 1 Synthesis Of Complexes 1 Andmentioning

confidence: 99%

Synthesis, Characterization, and Reactivity of the Group 11 Hydrido Clusters [Ag₆H₄(dppm)₄(OAc)₂] and [Cu₃H(dppm)₃(OAc)₂]

2016

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ABSTRACT:The group 11 hydride clusters [Ag 6 H 4 (dppm) 4 (OAc) 2 ](1) and(2) (dppm = 1,1-bis(diphenylphosphino)methane) were synthesized in moderate yields from the reaction of M(OAc) (M = Ag, Cu) with Ph 2 SiH 2 , in the presence of dppm. Complex 1 is the first structurally characterized homometallic polyhydrido silver cluster to be isolated. Both 1 and 2 catalyze the hydrosilylation of (,-unsaturated) ketones. Notably, this represents the first example of hydrosilylation with an authentic silver hydride complex.

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Highly Chemoselective Catalytic Hydrogenation of Unsaturated Ketones and Aldehydes to Unsaturated Alcohols Using Phosphine-Stabilized Copper(I) Hydride Complexes

Cited by 146 publications

References 37 publications

Copper-catalyzed asymmetric conjugate reduction as a route to novel β-azaheterocyclic acid derivatives

Copper-catalyzed asymmetric conjugate reduction as a route to novel β-azaheterocyclic acid derivatives

Nickel-accelerated addition of dialkylzinc reagents to aldehydes. Application to enantioselective synthesis

Synthesis, Characterization, and Reactivity of the Group 11 Hydrido Clusters [Ag₆H₄(dppm)₄(OAc)₂] and [Cu₃H(dppm)₃(OAc)₂]

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Highly Chemoselective Catalytic Hydrogenation of Unsaturated Ketones and Aldehydes to Unsaturated Alcohols Using Phosphine-Stabilized Copper(I) Hydride Complexes

Cited by 146 publications

References 37 publications

Copper-catalyzed asymmetric conjugate reduction as a route to novel β-azaheterocyclic acid derivatives

Copper-catalyzed asymmetric conjugate reduction as a route to novel β-azaheterocyclic acid derivatives

Nickel-accelerated addition of dialkylzinc reagents to aldehydes. Application to enantioselective synthesis

Synthesis, Characterization, and Reactivity of the Group 11 Hydrido Clusters [Ag6H4(dppm)4(OAc)2] and [Cu3H(dppm)3(OAc)2]

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Synthesis, Characterization, and Reactivity of the Group 11 Hydrido Clusters [Ag₆H₄(dppm)₄(OAc)₂] and [Cu₃H(dppm)₃(OAc)₂]