Stereochemical inversion of rim-differentiated pillar[5]arene molecular swings

Ke Du; Paul Demay-Drouhard; Kushal Samanta; Shunshun Li; Tushar Ulhas Thikekar; Haiying Wang; Minjie Guo; Barend Van Lagen; Han Zuilhof; Andrew C.H. Sue

doi:10.1021/acs.joc.0c01464

Stereochemical inversion of rim-differentiated pillar[5]arene molecular swings

Ke Du
, Paul Demay-Drouhard
, Kushal Samanta
, Shunshun Li
, Tushar Ulhas Thikekar
, Haiying Wang
, Minjie Guo
, Barend Van Lagen
, Han Zuilhof^*
, Andrew C.H. Sue^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

36 Citations (Scopus)

Abstract

To investigate the dynamic stereochemical inversion behavior of pillar[5]arenes (P[5]s) in more detail, we synthesized a series of novel rim-differentiated P[5]s with various substituents and examined their rapid rotations by variable-temperature NMR (203-298 K). These studies revealed for the first time the barrier of "methyl-through-the-annulus"rotation (ΔG‡ = 47.4 kJ·mol-1 in acetone) and indicated that for rim-differentiated P[5]s with two types of alkyl substituents, the smaller rim typically determines the rate of rotation. However, substituents with terminal CC or CC bonds give rise to lower inversion barriers, presumably as a result of attractive π-πinteractions in the transition state. Finally, data on a rim-differentiated penta-methyl-penta-propargyl P[5] exhibited the complexity of the overall inversion dynamics.

Original language	English
Pages (from-to)	11368-11374
Number of pages	7
Journal	Journal of Organic Chemistry
Volume	85
Issue number	17
DOIs	https://doi.org/10.1021/acs.joc.0c01464
Publication status	Published - 4 Sept 2020

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https://edepot.wur.nl/533331Licence: CC BY-NC-ND

CCDC 1989352: Experimental Crystal Structure Determination
Du, K. (Creator), Demay-Drouhard, P. (Creator), Samanta, K. (Creator), Li, S. (Creator), Thikekar, T. U. (Creator), Wang, H. (Creator), Guo, M. (Creator), Van Lagen, B. (Creator), Zuilhof, H. (Creator) & Sue, A. C. H. (Creator), Tianjin University, 10 Mar 2020
DOI: 10.5517/ccdc.csd.cc24s2np
Dataset
CCDC 1896020: Experimental Crystal Structure Determination
Du, K. (Creator), Demay-Drouhard, P. (Creator), Samanta, K. (Creator), Li, S. (Creator), Thikekar, T. U. (Creator), Wang, H. (Creator), Guo, M. (Creator), Van Lagen, B. (Creator), Zuilhof, H. (Creator) & Sue, A. C. H. (Creator), Tianjin University, 10 Mar 2020
DOI: 10.5517/ccdc.csd.cc21myyl
Dataset

Cite this

@article{808e5f412efe4a8ba4da093d1ea03df9,

title = "Stereochemical inversion of rim-differentiated pillar[5]arene molecular swings",

abstract = "To investigate the dynamic stereochemical inversion behavior of pillar[5]arenes (P[5]s) in more detail, we synthesized a series of novel rim-differentiated P[5]s with various substituents and examined their rapid rotations by variable-temperature NMR (203-298 K). These studies revealed for the first time the barrier of {"}methyl-through-the-annulus{"}rotation (ΔG‡ = 47.4 kJ·mol-1 in acetone) and indicated that for rim-differentiated P[5]s with two types of alkyl substituents, the smaller rim typically determines the rate of rotation. However, substituents with terminal CC or CC bonds give rise to lower inversion barriers, presumably as a result of attractive π-πinteractions in the transition state. Finally, data on a rim-differentiated penta-methyl-penta-propargyl P[5] exhibited the complexity of the overall inversion dynamics. ",

author = "Ke Du and Paul Demay-Drouhard and Kushal Samanta and Shunshun Li and Thikekar, \{Tushar Ulhas\} and Haiying Wang and Minjie Guo and \{Van Lagen\}, Barend and Han Zuilhof and Sue, \{Andrew C.H.\}",

year = "2020",

month = sep,

day = "4",

doi = "10.1021/acs.joc.0c01464",

language = "English",

volume = "85",

pages = "11368--11374",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society (ACS)",

number = "17",

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TY - JOUR

T1 - Stereochemical inversion of rim-differentiated pillar[5]arene molecular swings

AU - Du, Ke

AU - Demay-Drouhard, Paul

AU - Samanta, Kushal

AU - Li, Shunshun

AU - Thikekar, Tushar Ulhas

AU - Wang, Haiying

AU - Guo, Minjie

AU - Van Lagen, Barend

AU - Zuilhof, Han

AU - Sue, Andrew C.H.

PY - 2020/9/4

Y1 - 2020/9/4

N2 - To investigate the dynamic stereochemical inversion behavior of pillar[5]arenes (P[5]s) in more detail, we synthesized a series of novel rim-differentiated P[5]s with various substituents and examined their rapid rotations by variable-temperature NMR (203-298 K). These studies revealed for the first time the barrier of "methyl-through-the-annulus"rotation (ΔG‡ = 47.4 kJ·mol-1 in acetone) and indicated that for rim-differentiated P[5]s with two types of alkyl substituents, the smaller rim typically determines the rate of rotation. However, substituents with terminal CC or CC bonds give rise to lower inversion barriers, presumably as a result of attractive π-πinteractions in the transition state. Finally, data on a rim-differentiated penta-methyl-penta-propargyl P[5] exhibited the complexity of the overall inversion dynamics.

AB - To investigate the dynamic stereochemical inversion behavior of pillar[5]arenes (P[5]s) in more detail, we synthesized a series of novel rim-differentiated P[5]s with various substituents and examined their rapid rotations by variable-temperature NMR (203-298 K). These studies revealed for the first time the barrier of "methyl-through-the-annulus"rotation (ΔG‡ = 47.4 kJ·mol-1 in acetone) and indicated that for rim-differentiated P[5]s with two types of alkyl substituents, the smaller rim typically determines the rate of rotation. However, substituents with terminal CC or CC bonds give rise to lower inversion barriers, presumably as a result of attractive π-πinteractions in the transition state. Finally, data on a rim-differentiated penta-methyl-penta-propargyl P[5] exhibited the complexity of the overall inversion dynamics.

U2 - 10.1021/acs.joc.0c01464

DO - 10.1021/acs.joc.0c01464

M3 - Article

AN - SCOPUS:85090486019

SN - 0022-3263

VL - 85

SP - 11368

EP - 11374

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 17

ER -

Stereochemical inversion of rim-differentiated pillar[5]arene molecular swings

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Datasets

CCDC 1989352: Experimental Crystal Structure Determination

CCDC 1896020: Experimental Crystal Structure Determination

Cite this