Reductive Electrochemical Silylation of Unsaturated Nitrogen Functionalities: A Simple and Efficient Synthesis of Precursors of Bis(trimethylsilyl)methylamine

Grelier, Stéphane; Constantieux, Thierry; Deffieux, Denis; Bordeau, M.; Dunoguès, J.; Picard, Jean‐Paul; Palomo, Claudio; Aizpurua, J. M.

doi:10.1021/om00021a051

Cited by 13 publications

(5 citation statements)

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“…A few years ago, we published the synthesis of 2 through the reductive silylation of O -trimethylsilyl-protected cyanohydrins 3 by means of lithium in the presence of trimethylsilyl chloride in tetrahydrofuran (THF). , The key point was the decisive and unavoidable use of hexamethylphosphoramide (HMPA) as a cosolvent, which made the transformation complete. However, having gained experience in electroreductive silylation, we tested this technique (sacrificial anode) with the aim to avoid the use of lithium, on the one side, and to try to limit the amount of HMPA, on the other.…”

Section: Resultsmentioning

confidence: 99%

“…Electrochemical Reductive Silylation of 3: Synthesis of 2. The electrolysis procedure has already been published …”

Section: Methodsmentioning

confidence: 99%

“…The electrolysis procedure has already been published. 9 Using the equipment described, cyanohydrins 3 (150 mM) were mixed with THF (150 mL), trimethylsilyl chloride (240 g, 2.3 M, 300 mL), HMPA (36 g, 0.2 M, 40 mL), and tetrabutylammonium bromide (300 mg). After 4.4 faradays/mol were passed into the 500 mL undivided cell equipped with an aluminum-made sacrificial anode, the organic layer was extracted with dry pentane (500 mL).…”

Section: Methodsmentioning

confidence: 99%

“…11,12 The key point was the decisive and unavoidable use of hexamethylphosphoramide (HMPA) as a cosolvent, which made the transformation complete. However, having gained experience in electroreductive silylation, 9 we tested this technique (sacrificial anode) 13 with the aim to avoid the use of lithium, on the one side, and to try to limit the amount of HMPA, on the other.…”

Section: Synthesis Of Enaminesmentioning

confidence: 99%

“…If preparative methods exist for (aminomethyl)silanes [ m ono( s ilyl m ethyl) a mines, “MSMA”, ⋮SiCH 2 NH 2 ], α-silylbenzylamines [ a ryl( s ilyl) m ethyl a mines, “ASMA”, Ar(⋮Si)CHNH 2 ], or b is( s ilyl) m ethyl a mines [“BSMA”, (⋮Si) 2 CHNH 2 ], − general synthetic methods for α-silylalkylamines [ a lkyl( s ilyl) m ethyl a mines, “RSMA”, R(⋮Si)CHNH 2 ], 1 , were lacking. Only the preparation of one such RSMA, by alkylation of an (aminomethyl)silane, has been described in the literature …”

Section: Introductionmentioning

confidence: 99%

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Enamines of Acylsilanes: Electrochemical Synthesis, Structure, and Use as a Source of α-(Trimethylsilyl)alkylamines

Constantieux

Picard

1996

Organometallics

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R-(Trimethylsilyl)alkylamines ("RSMA"), 1, have been prepared with good yields from enamines of acylsilanes, 2, through reduction of the corresponding iminium salts, 5, with sodium borohydride. The entire process constitutes an original way to homologate a carbonyl compound into the next RSMA, as the starting enamine was obtained through reductive silylation of the O-silyl-protected cyanohydrin, 3, of this carbonyl compound. In this occasion, the electrochemical procedure for the reductive silylation was proven to be as effective as the chemical one, giving 2 in yields of the same order of magnitude. 29 Si NMR spectroscopic studies allowed the complete assignment of the E and Z structures of these isomeric enamines.

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Section: Resultsmentioning

confidence: 99%

“…Electrochemical Reductive Silylation of 3: Synthesis of 2. The electrolysis procedure has already been published …”

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Synthesis Of Enaminesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Enamines of Acylsilanes: Electrochemical Synthesis, Structure, and Use as a Source of α-(Trimethylsilyl)alkylamines

Constantieux

Picard

1996

Organometallics

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Asymmetric Synthesis of β‐Lactams by theStaudinger Reaction

et al. 2018

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In the century since Staudinger first reported the [2 + 2] cycloaddition reaction between a ketene and an imine to produce a β‐lactam, many variants, including highly stereoselective versions, have appeared that demonstrate a reliable and versatile transformation which has become the major synthetic entry to β‐lactams and products derived therefrom. Important advances have been made towards understanding the reaction mechanism, which in most cases is a stepwise process, as well as defining the variables which influence stereoselectivity. Successful diastereocontrol of the reaction can be achieved by using chiral auxiliaries attached at the ketene or the imine component, with diastereomeric ratios often above 95:5. Although most stereoselective methods afford β‐lactams with the 3,4‐ cis relative configuration, procedures to generate both monocyclic and bicyclic β‐lactams possessing the 3,4‐ trans configuration are also available. Whereas most current Staudinger protocols employ preformed imines, ketenes tend to be unstable and therefore are usually prepared in situ through dehydrohalogenation of acid chlorides by treatment with an excess of a tertiary amine base, or by in situ activation of carboxylic acids. Alternatively, stereoselective Staudinger reactions involving ketene generation by photolysis of Fisher chromium–carbene complexes or the Wolff rearrangement of α‐diazo carbonyl compounds are also viable. By this methodology stereoisomerically enriched β‐lactams can be prepared with a range of substitution patterns at the N1, C2, and C3 positions. The majority of the Staudinger reaction variants involve the synthesis of 3‐amino‐ and 3‐oxy‐β‐lactams, with fewer examples of 3‐halo‐, 3‐thio‐, or 3‐carbon‐substituted analogues. This chapter also describes applications of the Staudinger reaction to the synthesis of some important β‐lactam and non‐β‐lactam products.

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Electrochemistry of Organosilicon Compounds

Fuchigami

2009

Patai's Chemistry of Functional Groups

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Reductive Electrochemical Silylation of Unsaturated Nitrogen Functionalities: A Simple and Efficient Synthesis of Precursors of Bis(trimethylsilyl)methylamine

Cited by 13 publications

References 2 publications

Enamines of Acylsilanes: Electrochemical Synthesis, Structure, and Use as a Source of α-(Trimethylsilyl)alkylamines

Enamines of Acylsilanes: Electrochemical Synthesis, Structure, and Use as a Source of α-(Trimethylsilyl)alkylamines

Asymmetric Synthesis of β‐Lactams by theStaudinger Reaction

Electrochemistry of Organosilicon Compounds

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