Synthesis of E-vinylogous (R)-amino acid derivatives via metal-catalyzed allylic substitutions on enzyme-derived substrates

Deardorff, Donald R.; Taniguchi, Cullen M.; Nelson, Anna C.; Pace, Andrew; Kim, Alexander J.; Pace, Aaron; Jones, R. A.; Tafti, Sanaz A.; Nguyen, Charles; O’Connor, Caitlin; Tang, J.; Chen, Judy

doi:10.1016/j.tetasy.2005.03.018

Cited by 21 publications

(33 citation statements)

References 52 publications

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“…Similarly as indicated above, the relative E configuration of 4 or 6 was established on the basis of the value of the 1 H NMR coupling constant between the olefinic protons 11. The spectroscopic data of compounds 4a ,3c,3d,16 4c ,17 6 R 4g,4k and 6 S 4f are in agreement with those previously reported in the literature.…”

Section: Resultssupporting

confidence: 91%

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Highly Selective Synthesis of Enantiopure (S,E)‐α,β‐Unsaturated γ‐Amino Esters Through a Sequential Reaction of Ethyl Dibromoacetate with α‐Amino Aldehydes Promoted by Chromium Dichloride

Concellón¹,

Mejica²

2007

Eur J Org Chem

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A sequential reaction of ethyl dibromoacetate with various enantiopure N,N‐dibenzyl‐ or N‐Boc‐α‐amino aldehydes (derived from natural α‐amino acids), promoted by chromium dichloride, afforded optically active (S,E)‐α,β‐unsaturated γ‐amino esters. The C=C double bond was generated with total or very high E‐selectivity and the (S,E)‐α,β‐unsaturated γ‐amino esters were obtained with complete enantiomeric purity, except from N‐Boc‐phenylalaninal (as determined by chiral HPLC). A mechanism is proposed to explain this transformation. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Section: Resultssupporting

confidence: 91%

“…Ethyl ( S , E )‐4‐( tert ‐Butoxycarbonylamino)pent‐2‐enoate 3c,3d,16 (4a): Yellow oil. [ α ] D 25 = –17.2 ( c = 0.7, CHCl 3 ).…”

Section: Methodsmentioning

confidence: 99%

Highly Selective Synthesis of Enantiopure (S,E)‐α,β‐Unsaturated γ‐Amino Esters Through a Sequential Reaction of Ethyl Dibromoacetate with α‐Amino Aldehydes Promoted by Chromium Dichloride

Concellón¹,

Mejica²

2007

Eur J Org Chem

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“…( S )‐2‐(Methoxycarbonyloxy)‐4‐phenylbutanenitrile (7p): 4c,31 Colorless oil. [ α ] D 25 = –14.9 ( c = 4.1, CHCl 3 ) (58 % ee from GC, WCOT γ‐CD, FS‐Lipodex‐E stationary phase, T injector = 250 °C, T detector = 260 °C, T column = 90 °C, 10 min and 180 °C final temperature, rate 10 °C min –1 , P = 100 kPa, t r = 44.7 and 45 .…”

Section: Methodsmentioning

confidence: 99%

Enantioselective Synthesis of O‐Methoxycarbonyl Cyanohydrins: Chiral Building Blocks Generated by Bifunctional Catalysis with BINOLAM‐AlCl

et al. 2006

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Keywords: Cyanohydrin derivatives / Bifunctional catalysis / Asymmetric synthesis / BINOLAM / Aluminium (R)-or (S)-BINOLAM-AlCl, generated in situ, work as bifunctional catalysts in promoting the enantioselective cyanoalkoxycarbonylation of aldehydes. The reaction is wide in scope and the mechanistic evidence gathered suggests the intervention of an indirect process involving enantioselective hydrocyanation by HCN, followed by O-alkoxycarbonylation. The resultant O-alkoxycarbonyl cyanohydrins are shown to be important chiral building blocks for synthesis.

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“…The procedure was adapted from the literature. 17 To a solution of 2.6 g of potassium cyanide (38.9 mmol) in 20 mL of water at 0 o C was added sufficient concentrated HCl to attain a pH of 1. This solution was extracted with diisopropyl ether (3 x 15 mL) and the combine extracts kept at 0 o C. To a second 125 mL Erlenmeyer flask with a stir bar was added 3.6 g almond meal 18 and it was wetted with 5 mL of a 0.02 M pH 5.5 citrate buffer.…”

Section: (Step 1)mentioning

confidence: 99%

Rhenium-Catalyzed 1,3-Isomerization of Allylic Alcohols: Scope and Chirality Transfer

2006

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The scope of the triphenylsilyl perrhennate (O3ReOSiPh3, 1) catalyzed 1,3-isomerization of allylic alcohols has been thoroughly explored. It was found to be effective for a wide variety of secondary and tertiary allylic alcohol substrates bearing aryl, alkyl, and cyano substituents. Two general reaction types were found which gave high levels of product selectivity: those driven by formation of an extended conjugated system and those driven by selective silylation of a particular isomer. The efficiency of chirality transfer with various substrates was investigated, and conditions were found in which secondary and tertiary allylic alcohols could be formed with high levels of enantioselectivity. Consideration of selectivity trends with respect to the nature of the substituents around the allylic system revealed that this is a reliable and predictable method for allylic alcohol synthesis.

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Synthesis of E-vinylogous (R)-amino acid derivatives via metal-catalyzed allylic substitutions on enzyme-derived substrates

Cited by 21 publications

References 52 publications

Highly Selective Synthesis of Enantiopure (S,E)‐α,β‐Unsaturated γ‐Amino Esters Through a Sequential Reaction of Ethyl Dibromoacetate with α‐Amino Aldehydes Promoted by Chromium Dichloride

Highly Selective Synthesis of Enantiopure (S,E)‐α,β‐Unsaturated γ‐Amino Esters Through a Sequential Reaction of Ethyl Dibromoacetate with α‐Amino Aldehydes Promoted by Chromium Dichloride

Enantioselective Synthesis of O‐Methoxycarbonyl Cyanohydrins: Chiral Building Blocks Generated by Bifunctional Catalysis with BINOLAM‐AlCl

Rhenium-Catalyzed 1,3-Isomerization of Allylic Alcohols: Scope and Chirality Transfer

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