2,5-Diketopiperazines, new chiral auxiliaries for asymmetric Diels-Alder reactions

Le, Thuy X.; Bussolari, Jacqueline C.; Murray, William V.

doi:10.1016/s0040-4039(97)00769-7

Cited by 23 publications

(11 citation statements)

References 7 publications

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“…Chiral auxiliaries are almost always designed to have an aromatic moiety (Westwell and Williams, 1997). In one case, where R-prolyl-S-phenylalanyl is the auxiliary moiety, the phenyl group can stack partially over the vinyl dienophilic substituent, but it is also in position to stabilize the aromatic features of the reaction intermediate, or to interact directly as a transient reaction participant (Le et al, 1997). Another example furthers the notion that bacteriorhodopsin and the photoactive yellow protein might act via a pericyclic mechanism: in Diels-Alder condensations of small dienophiles with a naphthol-anthracenophane, there is a seemingly unlikely tendency of the dienophiles to attack the anthracene moiety by insertion between the two wings of the molecular V of the anthracenophane rather than from the outside (Mataka et al, 1995).…”

Section: Discussionmentioning

confidence: 99%

Protein-Assisted Pericyclic Reactions: An Alternate Hypothesis for the Action of Quantal Receptors

Radding

Romo

Phillips

1999

Biophysical Journal

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The rules for allowable pericyclic reactions indicate that the photoisomerizations of retinals in rhodopsins can be formally analogous to thermally promoted Diels-Alder condensations of monoenes with retinols. With little change in the seven-transmembrane helical environment these latter reactions could mimic the retinal isomerization while providing highly sensitive chemical reception. In this way archaic progenitors of G-protein-coupled chemical quantal receptors such as those for pheromones might have been evolutionarily plagiarized from the photon quantal receptor, rhodopsin, or vice versa. We investigated whether the known structure of bacteriorhodopsin exhibited any similarity in its active site with those of the two known antibody catalysts of Diels-Alder reactions and that of the photoactive yellow protein. A remarkable three-dimensional motif of aromatic side chains emerged in all four proteins despite the drastic differences in backbone structure. Molecular orbital calculations supported the possibility of transient pericyclic reactions as part of the isomerization-signal transduction mechanisms in both bacteriorhodopsin and the photoactive yellow protein. It appears that reactions in all four of the proteins investigated may be biological analogs of the organic chemists' chiral auxiliary-aided Diels-Alder reactions. Thus the light receptor and the chemical receptor subfamilies of the heptahelical receptor family may have been unified at one time by underlying pericyclic chemistry.

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Section: Discussionmentioning

confidence: 99%

Protein-Assisted Pericyclic Reactions: An Alternate Hypothesis for the Action of Quantal Receptors

Radding

Romo

Phillips

1999

Biophysical Journal

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“…The introduction of a tertiary hydroxy group in substrate 14 was effected by the sequential treatment of lactone 10 with potassium bis(trimethylsilyl)amide (KHMDS) and O 2 in the presence of PA C H T U N G T R E N N U N G (OEt) 3 , [21] thereby affording compound 14 in 82 % yield. Subsequent stereoselective reduction of compound 14 with LiAlH 4 provided lactal 9, which was treated with the Wittig-Horner reagent ((EtO) 2 P(O)CH 2 COOEt) in the presence of tBuOK to give the desired product (8) in 50 % yield.…”

Section: Synthesis Of the Abc Moietymentioning

confidence: 99%

Diastereoselective Total Synthesis of (±)‐Schindilactone A, Part 1: Construction of the ABC and FGH Ring Systems and Initial Attempts to Construct the CDEF Ring System

Sun

Ren

Xiao

et al. 2012

Chemistry An Asian Journal

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First-generation synthetic strategies for the diastereoselective total synthesis of schindilactone A (1) are presented and methods for the synthesis of the ABC, FGH, and CDEF moieties are explored. We have established a method for the synthesis of the ABC moiety, which included both a Diels-Alder reaction and a ring-closing metathesis as the key steps. We have also developed a method for the synthesis of the FGH moiety, which involved the use of a Pauson-Khand reaction and a carbonylative annulation reaction as the key steps. Furthermore, we have achieved the construction of the central 7-8 bicyclic ring system by using a [3,3]-rearrangement as the key step. However, unfortunately, when this rearrangement reaction was applied to the construction of the more advanced CDEF moiety, the anticipated annulation reaction did not occur and the development of an alternative synthetic strategy would be required for the construction of this central core.

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“…254 Other new agents include cis,cis-spiro- [4,4]nonane-1,6-diol, 255 monobenzylated isosorbide, 256 new sultams derived from cyclopentadiene 257 and diketopiperazines such as cyclo-(S)-phenylalanyl-(R)-proline. 258 Electronic control of π-stacking in 8-phenylmenthyl acrylates has been achieved using chromium carbonyl chemistry-the diastereomeric excess of the major endo adduct is clearly a function of the electron donor capacity of the complexed arene. 259 It is difficult to deliberately perform asymmetric exo-selective Diels-Alder reactions, but using chiral tungsten carbene complexes Wulff has been successful (Scheme 83).…”

Section: Asymmetric Intermolecular Reactionsmentioning

confidence: 99%

Cycloadditions in synthesis

Dell¹

1998

J. Chem. Soc., Perkin Trans. 1

113

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2,5-Diketopiperazines, new chiral auxiliaries for asymmetric Diels-Alder reactions

Cited by 23 publications

References 7 publications

Protein-Assisted Pericyclic Reactions: An Alternate Hypothesis for the Action of Quantal Receptors

Protein-Assisted Pericyclic Reactions: An Alternate Hypothesis for the Action of Quantal Receptors

Diastereoselective Total Synthesis of (±)‐Schindilactone A, Part 1: Construction of the ABC and FGH Ring Systems and Initial Attempts to Construct the CDEF Ring System

Cycloadditions in synthesis

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