<i>N</i>‐Sulfinyl Amines as a Nitrogen Source in the Asymmetric Intramolecular Aza‐Michael Reaction: Total Synthesis of (−)‐Pinidinol

Fustero, Santos; Monteagudo, Silvia; Sánchez‐Roselló, María; Flores, Sonia; Barrio, Pablo; Pozo, Carlos del

doi:10.1002/chem.201000615

Cited by 78 publications

(56 citation statements)

References 50 publications

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“…[51] It was shown that the process was reversible and that the stereoselectivity varied with the reaction conditions. With tBuOK at room temperature, formation of the thermodynamic product 33a was favored and a 33a/33b = 85:15 ratio was obtained.…”

Section: N-acylation Of Tert-butanesulfinamidesmentioning

confidence: 99%

“…[51] Similarly to the case of α-β-unsaturated ketones, the addition is reversible and the sense of stereoinduction varies with the reaction temperature. Thus, at -40°C, the cyclization of substrate 38 leads to the kinetic product 39b in an excellent 39a/39b = 06:94 ratio, while at room temperature, 39a is formed as major product, albeit with very low diastereomeric excess.…”

Section: N-acylation Of Tert-butanesulfinamidesmentioning

confidence: 99%

“…[51] Cyclization of 48 occurred most efficiently in the presence of tBuOK at room temperature and yielded a mixture of diastereomeric piperidines 49a and 49b in 49a/49b = 88:12 ratio. By contrast with the above-described five-membered ring closure leading to pyrrolidines 33a/33b, no variation of the stereoselectivity was observed upon modification of the reaction conditions (temperature, base or solvent).…”

Section: Equatorial Position and Not A Pseudo-axial One (Scheme 8)mentioning

confidence: 99%

“…The synthetic value of this method is well evidenced with the cyclization of 50 to obtain 51 that has been used in natural product synthesis. [51] Piperidine formation is also readily achieved by intramolecular aza-Michael reaction of tert-butanesulfinamides with tethered acrylates and occurs with excellent states (M5 versus M6) wherein the sulfinyl group and the free hydroxyethyl group are hydrogen-bonded. Cyclization through transition state model M5 was proposed to be favored because non-bonding interacwere formed in good yields and excellent diastereoselectivity.…”

Section: Equatorial Position and Not A Pseudo-axial One (Scheme 8)mentioning

confidence: 99%

“…[57] To account for the observed stereoinduction, the authors proposed a kinetic-based model involving cyclization via two competitive transition levels of stereoinduction. [51] This approach has been very recently used to develop an asymmetric synthesis of quinolizidine 54, which was used for natural product synthesis (Scheme 11). [54] The approach involved as the first step the cyclization of diacrylate 52 in the presence of NaH that induced a desymmetrization process wherein two stereocenters were created.…”

Section: Equatorial Position and Not A Pseudo-axial One (Scheme 8)mentioning

confidence: 99%

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tert-Butanesulfinamides as Nitrogen Nucleophiles in Carbon–Nitrogen Bond Forming Reactions

Hernandez

Chemla

Ferreira

et al. 2016

Chimia

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The use of tert-butanesulfinamides as nitrogen nucleophiles in carbon-nitrogen bond forming reactions is reviewed. This field has grown in the shadow of the general interest in N-tert-butanesulfinyl imines for asymmetric synthesis and occupies now an important place in its own right in the chemistry of the chiral amine reagent tert-butanesulfinamide. This article provides an overview of the area and emphasizes recent contributions wherein the tert-butanesulfinamides act as chiral auxiliaries or perform as nitrogen donors in metal-catalyzed amination reactions.

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Section: N-acylation Of Tert-butanesulfinamidesmentioning

confidence: 99%

Section: N-acylation Of Tert-butanesulfinamidesmentioning

confidence: 99%

Section: Equatorial Position and Not A Pseudo-axial One (Scheme 8)mentioning

confidence: 99%

Section: Equatorial Position and Not A Pseudo-axial One (Scheme 8)mentioning

confidence: 99%

Section: Equatorial Position and Not A Pseudo-axial One (Scheme 8)mentioning

confidence: 99%

See 3 more Smart Citations

tert-Butanesulfinamides as Nitrogen Nucleophiles in Carbon–Nitrogen Bond Forming Reactions

Hernandez

Chemla

Ferreira

et al. 2016

Chimia

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Alkene Cross‐Metathesis Reactions

et al. 2021

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This chapter describes olefin cross‐metathesis (CM) reactions catalyzed by ruthenium, molybdenum, and tungsten complexes and surveys the literature from 1993 through 2020. Cross‐metathesis has been applied to the synthesis of a wide range of functionalized alkenes, including natural and biologically active products. Due to its simplicity and inherit atom economy, CM has found applications in the preparation of fine chemicals and various building blocks, and in transformations of biomass. Tandem reactions involving CM as the key step are also reviewed. Examples discussed in this chapter serve to illustrate how the reactivity of alkene substrates in CM depends on the presence of functional groups and steric congestion in the proximity of the reacting double bonds. A discussion of the mechanism of olefin metathesis is also included.

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Asymmetric Hydroamination and Reductive Amination in Total Synthesis

Ghorai

Tiwari

Bhattacharyya

2013

Stereoselective Synthesis of Drugs and Natural Products

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Asymmetric hydroamination (AHA) and asymmetric reductive amination (ARA) are one of the most popular strategies for enantioselective synthesis of chiral amines, which are very important from a synthetic and a biological point of view. The addition of the NH bond across an unsaturated CC bond is known as hydroamination. AHA is ideal for industrial processes as it is a 100% atom‐economic reaction and involves readily available substrates. For broadening its scope for a variety of substrates, many metal‐based as well as metal‐free catalytic systems have been developed for asymmetric hydroamination. Along with the synthesis of functionalized chiral amines, AHA has served as a key strategy in the synthesis of the core of various natural products like codeine, pseudodistomin, swainsonine and of drugs like pentazocine. Reductive amination is a widely used efficient synthetic protocol to install an amine group in place of a carbonyl group in an organic compound. The reaction proceeds through the formation of imine and subsequent one‐pot reduction of it to give the product amine. Use of a metal‐chiral ligand combination, chiral Brønsted acid or chiral organocatalyst, or chiral auxiliary in the reaction can give rise to chiral amine products that are often valuable synthetic intermediates en route to many drugs and natural products. Application of these protocols in the total synthesis of drugs and natural products will be discussed along with some experimental procedures.

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N‐Sulfinyl Amines as a Nitrogen Source in the Asymmetric Intramolecular Aza‐Michael Reaction: Total Synthesis of (−)‐Pinidinol

Cited by 78 publications

References 50 publications

tert-Butanesulfinamides as Nitrogen Nucleophiles in Carbon–Nitrogen Bond Forming Reactions

tert-Butanesulfinamides as Nitrogen Nucleophiles in Carbon–Nitrogen Bond Forming Reactions

Alkene Cross‐Metathesis Reactions

Asymmetric Hydroamination and Reductive Amination in Total Synthesis

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