Transition metal catalysed reactions of diazocompounds - part III a one-step synthesis of substituted furanes and esters.

Paulissen, R.; Hayez, E.; Hubert, Aurélia; Teyssié, Philippe

doi:10.1016/s0040-4039(01)82283-8

Cited by 72 publications

(25 citation statements)

References 2 publications

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“…The reactions were very fast and were completed within a few minutes (entries 1-3) with 0.1 mol % of 3 a as the catalyst. The use of 1 mol % of the catalyst with morpholine resulted in the formation of the desired product and the reaction proceeded much faster with the porphyrins than with the corrole (entries [4][5][6]. The use of porphyrin-based catalysts 3 a and 3 b to activate the primary amines alanine ethyl ester and propylamine was also fruitful and the expected products were obtained in high overall yields (entries 7-9).…”

Section: Wwwchemeurjorgmentioning

confidence: 99%

“…[5] These catalysts were overshadowed by [Rh 2 A C H T U N G T R E N N U N G (OAc) 4 ], developed as a catalyst in the 1970s by Paulissen et al [6] However, both the earlier and the more recently developed copper-, silver-, gold-, and ruthenium-based catalysts are usually required in amounts of 1 to 10 mol % and suffer from one or more of the following limitations: gradual addition of the diazo compound to avoid dimerization byproducts, gradual addition of the amine to avoid catalyst poisoning, long reaction times, and low-to-moderate chemical yields. [2,[7][8][9] Decade-long efforts were devoted to the development of catalysts for enantioselective metal-carbene insertion into N À H bonds.…”

Section: Introductionmentioning

confidence: 99%

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Iron(III) Corroles and Porphyrins as Superior Catalysts for the Reactions of Diazoacetates with Nitrogen‐ or Sulfur‐Containing Nucleophilic Substrates: Synthetic Uses and Mechanistic Insights

Aviv

Gross

2008

Chemistry A European J

130

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A thorough mechanistic investigation has been performed on the reactions of primary and secondary amines with diazoacetates, which proceed uniquely quickly and efficiently when catalyzed by iron(III) corroles and porphyrins. Two major differences in relation to other metal-based catalysts are that the iron complexes are not poisoned by excess amine and that metal-carbene intermediates are apparently not involved in the reaction pathway. The results instead point towards nitrogen ylide intermediates formed by nucleophilic attack of the amines on diazoacetate-coordinated iron complexes. Nitrogen ylides are also formed when allyl- and propargyl-substituted tertiary amines react with diazoacetates, a scenario that smoothly leads to 2,3-rearrangement reaction products with catalytic amounts of the iron(III) complexes. Similar findings regarding the superiority of the iron(III) complexes (in terms of catalyst loading, chemical yields, and reaction conditions) were obtained with thiols (S--H insertion) and sulfides (2,3-rearrangement reactions), which suggest similar mechanisms operate in these cases.

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Section: Wwwchemeurjorgmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Iron(III) Corroles and Porphyrins as Superior Catalysts for the Reactions of Diazoacetates with Nitrogen‐ or Sulfur‐Containing Nucleophilic Substrates: Synthetic Uses and Mechanistic Insights

Aviv

Gross

2008

Chemistry A European J

130

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“…Later Nicaud and Kagan employed chiral diazoesters and chiral amines to obtain roughly 25 % de in NH insertion reactions 10. The introduction of dirhodium(II) tetracarboxylates as efficient catalysts for NH insertion in 197411 led to an increase in the application of such reactions in synthesis; a notable early example was an intramolecular insertion into a β‐lactam NH bond, a key step in the Merck synthesis of thienamycin (Scheme ) 12. In the last 25 years, carbene NH insertion reactions have found increasing use, particularly in the synthesis of N‐containing heterocycles, developed in our laboratory and elsewhere.…”

Section: Methodsmentioning

confidence: 99%

Enantioselective Insertion of Metal Carbenes into NH Bonds: A Potentially Versatile Route to Chiral Amine Derivatives

Moody

2007

Angew Chem Int Ed

122

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amino acids · asymmetric synthesis · carbenes · diazo compounds · insertionThe formation of carbon-heteroatom bonds is one of the fundamental transformations of organic chemistry. One potentially powerful method is the insertion of metal carbenes, readily derived by transition-metal-catalyzed reactions of diazo compounds 1, into XÀH bonds (Scheme 1).[1]The reaction is a versatile route to a wide range of functionalized compounds 2 such as a-alkoxyesters, a-aminophosphonates, a-silylketones, and assumes even greater significance if it can be carried out in an asymmetric manner. Unfortunately, whilst asymmetric metal carbene CÀH insertion reactions have become a well-established part of synthetic methodology, [2] much less progress has been made with the X À H counterparts, although some success has been enjoyed in the arena of Si À H insertion using chiral dirhodium carboxylates or carboxamides, or copper-based catalyst systems.[3] The attainment of excellent enantioselectivities in metal carbene CÀH and SiÀH insertion reactions using chiral dirhodium or copper catalysts presumably reflects the reaction mechanism-a concerted insertion into the X À H bond. With more polar X À H bonds, other mechanisms such as formation of ylide intermediates by attack of the heteroatom lone pair on the electrophilic metal carbene may operate, [4]

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“…Early work relied on copper catalysts, 5 but it was the 1974 report that dirhodium(II) acetate was an extremely effective catalyst for such transformations, 6 that stimulated much of the subsequent work in the area. 7 However, the possibility that such N-H insertion reactions could be carried out stereoselectively to give α-amino acid derivatives as single enantiomers at the new stereocentre remains the most attractive aspect.…”

Section: Methodsmentioning

confidence: 99%

N-H Insertion reactions of rhodium carbenoids. Part 4. New chiral dirhodium(II) carboxylate catalysts

Buck¹,

Moody²,

Pepper³

2002

Arkivoc

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Transition metal catalysed reactions of diazocompounds - part III a one-step synthesis of substituted furanes and esters.

Cited by 72 publications

References 2 publications

Iron(III) Corroles and Porphyrins as Superior Catalysts for the Reactions of Diazoacetates with Nitrogen‐ or Sulfur‐Containing Nucleophilic Substrates: Synthetic Uses and Mechanistic Insights

Iron(III) Corroles and Porphyrins as Superior Catalysts for the Reactions of Diazoacetates with Nitrogen‐ or Sulfur‐Containing Nucleophilic Substrates: Synthetic Uses and Mechanistic Insights

Enantioselective Insertion of Metal Carbenes into NH Bonds: A Potentially Versatile Route to Chiral Amine Derivatives

N-H Insertion reactions of rhodium carbenoids. Part 4. New chiral dirhodium(II) carboxylate catalysts

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