Quantum mechanistic insights on aryl propargyl ether Claisen rearrangement

Srinivasadesikan, Venkatesan; Dai, Jiun-Kuang; Lee, Shyi‐Long

doi:10.1039/c4ob00388h

Cited by 17 publications

(19 citation statements)

References 49 publications

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“…The thermal cyclization of substituted aryl propargyl ethers by sigmatropic Claisen rearrangements has been described previously as a strategy for the synthesis of chromene derivatives,10 including bioactive natural products 10e,10f. Moreover, recent studies on the rearrangement of aryl propargyl ether to chromenes by theoretical DFT methods corroborate the mechanism proposal 10g…”

Section: Resultsmentioning

confidence: 75%

Pericyclic Reactions of Azafulvenium Methides Bearing Internal Dipolarophiles – Synthesis of Chromene and Chromane Derivatives

et al. 2015

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The reactivity of azafulvenium methides with internal dipolarophiles was explored as an approach to new chromene derivatives. 4,5‐Dimethoxycarbonyl‐ and 5‐ethoxycarbonyl‐4‐phenylazafulvenium methides with a prop‐2‐ynyloxyphenyl substituent are converted into 2‐[2‐(2H‐chromen‐8‐yl)vinyl]‐1H‐pyrroles through a sequence of rearrangements. 4,5‐Dimethoxycarbonylazafulvenium methide with a more‐activated dipolarophile as well as the more‐activated 5‐(trifluoromethyl)azafulvenium methide with an unactivated alkyne could be trapped by [8π+2π] cycloadditions to afford 8,12a‐dihydro‐6H‐chromeno[4,3‐e]indolizines. 5‐(Trifluoromethyl)azafulvenium methide with a 2‐(3‐methoxycarbonylprop‐2‐enyloxy)phenyl substituent at C‐1 participated in both intramolecular [8π+2π] and [4π+2π] cycloadditions to afford heterocycle‐fused chromanes. The microwave‐induced rearrangements of 3‐[2‐(prop‐2‐ynyloxy)phenyl]‐1H,3H‐pyrrolo[1,2‐c]thiazoles afforded chiral 3‐(2H‐chromen‐8‐yl)‐1H,3H‐pyrrolo[1,2‐c]thiazoles.

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Section: Resultsmentioning

confidence: 75%

Pericyclic Reactions of Azafulvenium Methides Bearing Internal Dipolarophiles – Synthesis of Chromene and Chromane Derivatives

et al. 2015

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“…[24] Lee and his coworkers made DFT calculations of reaction paths of the aryl propargyl ether rearrangement. [25,26] Rehbein et al reported a kinetic study on an uncatalyzed [3,3]-sigmatropic rearrangement, "Gosteli-Claisen Rearrangement," of 2-alkoxycarbonyl-substituted allyl vinyl ethers. [27] Houk and his coworkers made calculations of transition states of boat and chair conformations of Ireland-Claisen Rearrangements.…”

Section: Introductionmentioning

confidence: 99%

“…Using 2, 6‐dimethylphenyl propargyl ether and its derivatives, Zsindely and Schmidt reported the rearrangement and suggested its mechanism . Lee and his coworkers made DFT calculations of reaction paths of the aryl propargyl ether rearrangement . Rehbein et al reported a kinetic study on an uncatalyzed [3,3]‐sigmatropic rearrangement, “Gosteli‐Claisen Rearrangement,” of 2‐alkoxycarbonyl‐substituted allyl vinyl ethers .…”

Section: Introductionmentioning

confidence: 99%

The tautomerization and ring closure in the Claisen rearrangement: A DFT study

Yamabe

Yamazaki

2018

Int J of Quantum Chemistry

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Elementary processes of the aromatic Claisen rearrangement were investigated by DFT calculations. First, rearrangements of four substrates Ph—O—CH2—CHCH2 [A], Ph—O—CH2—CHCH(OMe) [B], Ph—O—CH2—CHCH2····BF3 [C], and Ph—O—CH—CHCH(OMe)····BF3 [D] were examined. In these systems, the tautomerization is initiated by the intermolecular proton transfer involving the transient ion‐pair intermediate. An ignition‐propagation chain‐reaction mechanism in the tautomerization was suggested. For [A], the (ortho‐allyl phenol → α‐methyl‐dihydrobenzofuran (α‐methyl‐cumarane)) process was found to be ready and the product of the Claisen rearrangement seems to be the cumarane rather than the phenol. In [D] (activated both by the terminal methoxy group and by the BF3 catalyst), not the [3,3]‐sigmatropic shift but the tautomerization is the rate determining step. Second, the parent system, Ph—O—CH2—CHCH2, was investigated with (H2O) n (n = 2, 4, 6, and 10) systematically. The tautomerization takes place by the proton transfer via the water dimer or trimer. Except n = 2, similar changes of Gibbs free energies were obtained from the ether substrate to the cumarane.

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“…All of the remaining NMR ( 13 C and HSQC) and MS data were in full agreement with the homocalix[3]arene[1]benzofuran structure of 4 . 9 …”

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confidence: 99%

“…In the literature, it is proposed that an aryl propargyl Claisen rearrangement usually proceeds through a first [3,3] sigmatropic migration, which leads to an allene intermediate. 9 Due to the entity of the system (C 40 H 44 O 4 ), all calculations were performed at the B3LYP level of theory employing the 6-31+G* basis set ( Supporting Information ). This combination, benchmarked versus several other DFT methods for the aryl propargyl ether Claisen rearrangement, gives the better performance in terms of CPU time and calculated activation energy.…”

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confidence: 99%

Unusual Calixarenes Incorporating Chromene and Benzofuran Moieties Obtained via Propargyl Claisen Rearrangement

et al. 2021

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Monopropargyloxy-tripropoxy-calix[4]arene 1 was subjected to a propargyl Claisen rearrangement to give unusual calix[3]arene[1]chromene and homocalix[3]arene[1]benzofuran macrocycles. Quantum mechanical density functional theory calculations indicated that an initial [3,3] sigmatropic reaction affords a highly reactive allene intermediate, stabilized by two main diradical pathways leading to six- and five-membered oxygenated rings. In the presence of a n -butylammonium guest, calix[3]arene[1]chromane 6 forms two stereoisomeric complexes stabilized by + N–H···O and cation···π interactions.

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Quantum mechanistic insights on aryl propargyl ether Claisen rearrangement

Cited by 17 publications

References 49 publications

Pericyclic Reactions of Azafulvenium Methides Bearing Internal Dipolarophiles – Synthesis of Chromene and Chromane Derivatives

Pericyclic Reactions of Azafulvenium Methides Bearing Internal Dipolarophiles – Synthesis of Chromene and Chromane Derivatives

The tautomerization and ring closure in the Claisen rearrangement: A DFT study

Unusual Calixarenes Incorporating Chromene and Benzofuran Moieties Obtained via Propargyl Claisen Rearrangement

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