Enantioselective formation of a dynamic hydrogen-bonded assembly based on the chiral memory concept

T.I. Ish-i Tsutomu, Mercedes Crego Calama, P. Timmerman, David Reinhoudt, Seiji Shinkai

    Research output: Contribution to journalArticleAcademicpeer-review

    74 Citations (Scopus)

    Abstract

    In this paper, we report the enantioselective formation of a dynamic noncovalent double rosette assembly 1a3·(CYA)6 composed of three 2-pyridylcalix[4]arene dimelamines (1a) and six butylcyanuric acid molecules (BuCYA). The six 2-pyridyl functionalities of the assembly interact stereoselectively with chiral dicarboxylic acids 3a-e via two-point hydrogen-bonding interactions. One of the two enantiomeric assemblies (P- or M-) 1a3·(CYA)6 is formed in excess as the result of the complexation of the chiral diacids, resulting in formation of optically active assemblies. The complexations with dibenzoly tartaric acids D-3a and L-3a (3 equivalent), respectively, leading to the formation of diastereomeric assemblies (P)-1a3·(BuCYA)6·(D-3a)3 and (M)-1a3·(BuCYA)6·(L-3a)3 with 90% diastereomeric excess. The diastereomeric excess in (M)-1a3·(BuCYA)6·(L-3a)3 is "memorized" when L-3a is removed by precipitation with ethlylenediamine (EDA). The assembly (M)-1a3·(BuCYA)6 is still optically active (90% enantiomeric excess), although none of its individual components are chiral. (M)-1a3·(BuCYA)6 has a high kinetic stability toward racemization (Ea = 119 kJ mol-1, half-life of (M)-1a3·(BuCYA)6 is ca. 1 week at 20°C).
    Original languageUndefined
    Pages (from-to)14631-14641
    JournalJournal of the American Chemical Society
    Volume124
    Issue number49
    DOIs
    Publication statusPublished - 2002

    Keywords

    • IR-38094
    • METIS-208736

    Cite this

    Ish-i Tsutomu, T.I. ; Crego Calama, Mercedes ; Timmerman, P. ; Reinhoudt, David ; Shinkai, Seiji. / Enantioselective formation of a dynamic hydrogen-bonded assembly based on the chiral memory concept. In: Journal of the American Chemical Society. 2002 ; Vol. 124, No. 49. pp. 14631-14641.
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    title = "Enantioselective formation of a dynamic hydrogen-bonded assembly based on the chiral memory concept",
    abstract = "In this paper, we report the enantioselective formation of a dynamic noncovalent double rosette assembly 1a3·(CYA)6 composed of three 2-pyridylcalix[4]arene dimelamines (1a) and six butylcyanuric acid molecules (BuCYA). The six 2-pyridyl functionalities of the assembly interact stereoselectively with chiral dicarboxylic acids 3a-e via two-point hydrogen-bonding interactions. One of the two enantiomeric assemblies (P- or M-) 1a3·(CYA)6 is formed in excess as the result of the complexation of the chiral diacids, resulting in formation of optically active assemblies. The complexations with dibenzoly tartaric acids D-3a and L-3a (3 equivalent), respectively, leading to the formation of diastereomeric assemblies (P)-1a3·(BuCYA)6·(D-3a)3 and (M)-1a3·(BuCYA)6·(L-3a)3 with 90{\%} diastereomeric excess. The diastereomeric excess in (M)-1a3·(BuCYA)6·(L-3a)3 is {"}memorized{"} when L-3a is removed by precipitation with ethlylenediamine (EDA). The assembly (M)-1a3·(BuCYA)6 is still optically active (90{\%} enantiomeric excess), although none of its individual components are chiral. (M)-1a3·(BuCYA)6 has a high kinetic stability toward racemization (Ea = 119 kJ mol-1, half-life of (M)-1a3·(BuCYA)6 is ca. 1 week at 20°C).",
    keywords = "IR-38094, METIS-208736",
    author = "{Ish-i Tsutomu}, T.I. and {Crego Calama}, Mercedes and P. Timmerman and David Reinhoudt and Seiji Shinkai",
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    year = "2002",
    doi = "10.1021/ja0207302",
    language = "Undefined",
    volume = "124",
    pages = "14631--14641",
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    Enantioselective formation of a dynamic hydrogen-bonded assembly based on the chiral memory concept. / Ish-i Tsutomu, T.I.; Crego Calama, Mercedes; Timmerman, P.; Reinhoudt, David; Shinkai, Seiji.

    In: Journal of the American Chemical Society, Vol. 124, No. 49, 2002, p. 14631-14641.

    Research output: Contribution to journalArticleAcademicpeer-review

    TY - JOUR

    T1 - Enantioselective formation of a dynamic hydrogen-bonded assembly based on the chiral memory concept

    AU - Ish-i Tsutomu, T.I.

    AU - Crego Calama, Mercedes

    AU - Timmerman, P.

    AU - Reinhoudt, David

    AU - Shinkai, Seiji

    N1 - 701

    PY - 2002

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    N2 - In this paper, we report the enantioselective formation of a dynamic noncovalent double rosette assembly 1a3·(CYA)6 composed of three 2-pyridylcalix[4]arene dimelamines (1a) and six butylcyanuric acid molecules (BuCYA). The six 2-pyridyl functionalities of the assembly interact stereoselectively with chiral dicarboxylic acids 3a-e via two-point hydrogen-bonding interactions. One of the two enantiomeric assemblies (P- or M-) 1a3·(CYA)6 is formed in excess as the result of the complexation of the chiral diacids, resulting in formation of optically active assemblies. The complexations with dibenzoly tartaric acids D-3a and L-3a (3 equivalent), respectively, leading to the formation of diastereomeric assemblies (P)-1a3·(BuCYA)6·(D-3a)3 and (M)-1a3·(BuCYA)6·(L-3a)3 with 90% diastereomeric excess. The diastereomeric excess in (M)-1a3·(BuCYA)6·(L-3a)3 is "memorized" when L-3a is removed by precipitation with ethlylenediamine (EDA). The assembly (M)-1a3·(BuCYA)6 is still optically active (90% enantiomeric excess), although none of its individual components are chiral. (M)-1a3·(BuCYA)6 has a high kinetic stability toward racemization (Ea = 119 kJ mol-1, half-life of (M)-1a3·(BuCYA)6 is ca. 1 week at 20°C).

    AB - In this paper, we report the enantioselective formation of a dynamic noncovalent double rosette assembly 1a3·(CYA)6 composed of three 2-pyridylcalix[4]arene dimelamines (1a) and six butylcyanuric acid molecules (BuCYA). The six 2-pyridyl functionalities of the assembly interact stereoselectively with chiral dicarboxylic acids 3a-e via two-point hydrogen-bonding interactions. One of the two enantiomeric assemblies (P- or M-) 1a3·(CYA)6 is formed in excess as the result of the complexation of the chiral diacids, resulting in formation of optically active assemblies. The complexations with dibenzoly tartaric acids D-3a and L-3a (3 equivalent), respectively, leading to the formation of diastereomeric assemblies (P)-1a3·(BuCYA)6·(D-3a)3 and (M)-1a3·(BuCYA)6·(L-3a)3 with 90% diastereomeric excess. The diastereomeric excess in (M)-1a3·(BuCYA)6·(L-3a)3 is "memorized" when L-3a is removed by precipitation with ethlylenediamine (EDA). The assembly (M)-1a3·(BuCYA)6 is still optically active (90% enantiomeric excess), although none of its individual components are chiral. (M)-1a3·(BuCYA)6 has a high kinetic stability toward racemization (Ea = 119 kJ mol-1, half-life of (M)-1a3·(BuCYA)6 is ca. 1 week at 20°C).

    KW - IR-38094

    KW - METIS-208736

    U2 - 10.1021/ja0207302

    DO - 10.1021/ja0207302

    M3 - Article

    VL - 124

    SP - 14631

    EP - 14641

    JO - Journal of the American Chemical Society

    JF - Journal of the American Chemical Society

    SN - 0002-7863

    IS - 49

    ER -