A new catalytic transformation of diazo esters: hydride abstraction in dirhodium(II)-catalysed reactions

Doyle, Michael P.; Dyatkin, Alexey B.; Autry, Christopher

doi:10.1039/p19950000619

Cited by 45 publications

(26 citation statements)

References 15 publications

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“…ee ester 30 (Eq. 3) [67]. Kinetic isotope data obtained from this work suggest that indanone 23 formation follows through a mechanism involving hydride abstraction by the intermediate rhodium-carbene.…”

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confidence: 88%

Rhodium(II)‐Catalyzed Oxidative Amination

Espino

Bois

2005

Modern Rhodium‐Catalyzed Organic Reactions

105

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17 Rhodium(II)-Catalyzed Oxidative Amination 380 Scheme 17.1 Copper-catalyzed decomposition of arylsulfonyl azides. Scheme 17.2 Intramolecular C-H amination of an iminoiodinane. 17.3 Intermolecular C-H Amination with Rhodium(II) Catalysts 381 Scheme 17.3 Metal porphyrin-catalyzed allylic amination. Scheme 17.4 C-H amination by a radical-rebound mechanism. 17 Rhodium(II)-Catalyzed Oxidative Amination 382 Scheme 17.5 Rhodium-catalyzed N-atom transfer using NsN=IPh. Scheme 17.6 Stereospecific C-H amination under rhodium-catalyzed conditions. 17.3 Intermolecular C-H Amination with Rhodium(II) Catalysts 383 Scheme 17.7 Radical clock study of metallo-nitrene C-H insertion. Scheme 17.8 Intermolecular C-H insertion by chiral rhodium catalysts. 17.5 Intramolecular C-H Amination with Rhodium(II) Catalysts 385 Scheme 17.11 Allylic and benzylic amination using PhI(OAc) 2 . 17.5 Intramolecular C-H Amination with Rhodium(II) Catalysts 387 Tab. 17.1 C-H amination of 18 carbamate esters. Entry Substrate Product Entry Substrate Product 17.5 Intramolecular C-H Amination with Rhodium(II) Catalysts 389 Scheme 17.14 Ketone formation by 28 alcohol-derived carbamates. 17.7 Enantioselective C-H Insertion with Sulfamate Esters 401 Scheme 17.29 Oxidative cyclization of unsaturated sulfonamides. Scheme 17.30 Preliminary investigations of asymmetric C-H amination. 17.11 Applications of C-H Amination in Synthesis 407 17.11 Applications of C-H Amination in Synthesis 409 Scheme 17.39 Asymmetric synthesis of (-)-tetrodotoxin. 17 Rhodium(II)-Catalyzed Oxidative Amination 410 Scheme 17.40 Nucleophilic ring opening of N-acylated oxathiazinanes. Scheme 17.41 Nickel-catalyzed cross-coupling of phenol-derived sulfamate esters.

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confidence: 88%

Rhodium(II)‐Catalyzed Oxidative Amination

Espino

Bois

2005

Modern Rhodium‐Catalyzed Organic Reactions

105

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“…Although these byproducts were not formed in high yields, they are ubiquitous in catalytic reactions of tetrahydropyranone- and tetrahydrofuranone-diazoacetoacetates. 17 …”

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confidence: 99%

Competitive [2,3]- and [1,2]-Oxonium Ylide Rearrangements. Concerted or Stepwise?

et al. 2012

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The axial-equatorial conformational isomer distribution of the reactant diazoacetoacetate or its metal carbene intermediate is reflected in Rh(II) catalyzed oxonium ylide forming reactions of 3-(trans-2-arylvinyl)tetrahydropyranone- 5-diazoacetoacetates that afford diastereoisomeric products for both the symmetry-allowed [2,3]- and the formally symmetry-forbidden [1,2]-oxonium ylide rearrangements.

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“…For reaction of diazoketone 1h (Table 1, entry 9), the b-hydrogen is activated by two adjacent phenyl substituents and it is likely that hydride abstraction 28,29 competes with the aromatic addition process accounting for the low yields of 6h recorded. Once this hydrogen is replaced by a methyl group in diazoketone 1i (Table 1, entry 10), the efficiency of the aromatic addition reaction is restored.…”

Section: Resultsmentioning

confidence: 98%

“…This is consistent with previous results outlined by Doyle for the aromatic addition of biaryl diazoacetamides. 29,30 On treatment of a-diazoketones 3 with the standard catalyst, Rh 2 (OAc) 4 , excellent diastereocontrol was observed, with a ratio of >98:2 (cis/trans) observed for each of the diazoketones 3aeg examined. As observed earlier with the b-substituted series 1, decreased diastereocontrol is observed through use of the more reactive catalysts Rh 2 (pfb) 4 , Rh 2 (tfa) 4 and Rh 2 (S-mand) 4 , as seen in the cyclisation of diazoketones 3b and 3c (Table 3, entries 2 and 3).…”

Section: Intramolecular Aromatic Addition Of A-substituted A-mentioning

confidence: 97%