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Synlett 2011(20): 3046-3052  
DOI: 10.1055/s-0031-1289904
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

An Eficient One-Pot Synthesis of Macrocyclic Compounds Possessing Propargylamine Skeletons via Mannich Reaction

Tao Pang, Qinwan Yang, Meng Gao, Meng Wang, Anxin Wu*
Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, Central China Normal University, Wuhan 430079, P. R. of China
e-Mail: chwuax@mail.ccnu.edu.cn;
Further Information

Publication History

Received 12 September 2011
Publication Date:
23 November 2011 (online)

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Abstract

A new efficient method using the Mannich three-component reaction in one pot to synthesize [1+2+1]- and [2+4+2]-macrocyclic compounds possessing a propargylamine backbone was reported. Interestingly, 1,4-diazepane as a multiuse reagent played the part of a substrate to participate in the Mannich reaction and acted as a base to promote the Eglinton-Glaser dimerizations in the coordination processes simultaneously via a one-pot procedure. The target macrocycles were obtained in good yields.

Key words

multicomponent reaction - one pot - dimerizations - macrocycles - coordination processes

    Primary data for this article are available online and can be cited using the following DOI: 10.4125/pd0023th:
  • Primary Data
12

Crystal Structure Data for Compound L1 CCDC 815275, C18H20N2O2; MW = 296.36; monoclinic; space group: P2 (1)/c, a = 10.715 (3), b = 5.4373 (13), c = 26.758 (6) Å, α = 90.00˚, β = 92.176 (4)˚, γ = 90.00˚; V = 1557.8 (6) ų; T = 150 (2) K; Z = 4; D C = 1.264 Mg/m³; µ = 0.083 mm-¹; λ = 0.71073 Å; F(000) = 632; crystal size: 0.16 × 0.10 × 0.10 mm³; 3376 independent reflections [R(int) = 0.0940], reflections collected 10246; refinement method: full-matrix least-squares on F²: goodness-of-fit on F² 1.093; final R indices [I > 2σ(I)], R1 = 0.0752, wR2 = 0.1847, largest diff. peak and hole 0.390 Å-³and
-0.242 e Å-³.

13

Crystal Structure Data for Compound L2 CCDC 848122, C36H38Cl2N4O4; MW = 661.60; triclinic; space group: P1, a = 7.6628 (19), b = 10.062 (3), c = 11.528 (3) Å, α = 91.301 (4)˚, β = 93.047 (4)˚, γ = 112.314 (4)˚; V = 820.2 (4) ų, T = 298 (2) K, Z = 1, D C = 1.339 Mg/m³, µ = 0.244 mm-¹, λ = 0.71073 Å, F(000) = 348; crystal size: 0.16 × 0.12 × 0.10 mm³; 2844 independent reflections [R(int) = 0.0183], reflections collected 4852; refinement method: full-matrix least-squares on F²: goodness-of-fit on F² 1.069; final R indices [I > 2σ(I)], R1 = 0.0706, wR2 = 0.1746, largest diff. peak and hole 0.273 Å-³and -0.278 e Å-³.

14

Crystal Structure Data for Compound S3 CCDC 832859, C27H30N2O2, MW = 414.53; monoclinic; space group: C2/c, a = 13.946 (2) Å, b = 18.635 (3) Å, c = 9.1650 (14) Å, α = 90.00˚, β = 107.492 (2)˚, γ = 90.00˚, V = 2271.6 (6) ų, T = 298 (2) K, Z = 4, D C = 1.212 Mg/m³, µ = 0.076 mm-¹, λ = 0.71073 Å, F(000) = 888; crystal size 0.16 × 0.12 × 0.10 mm³; 2471 independent reflections [R(int) = 0.0227], reflections collected 7122; refinement method: full-matrix least-squares on F²: goodness-of-fit on F² 1.137; final R indices [I > 2σ(I)], R1 = 0.0727, wR2 = 0.1597, largest diff. peak and hole 0.227 Å-³and
-0.151 e Å-³.

15

Crystal Structure Data for Compound S4 CCDC 815277, C24H24N2O2S, MW = 404.51; triclinic; space group: P1, a = 9.2569 (12), b = 10.8855 (14), c = 11.5162 (14) Å, α = 114.300(2)˚, β = 90.206 (2)˚, γ = 90.845 (2)˚, V = 1057.5 (2) ų, T = 298 (2) K, Z = 2, D C = 1.270 Mg/m³, µ = 0.175 mm-¹, λ = 0.71073Å, F(000) = 428; crystal size 0.16 × 0.12 × 0.10 mm³; 4075 independent reflections [R(int) = 0.0215], reflections collected 6108; refinement method: full-matrix least-squares on F²: goodness-of-fit on F² 1.062; final R indices [I > 2σ(I)], R1 = 0.0581, wR2 = 0.1311, largest diff. peak and hole 0.185 Å-³and
-0.186 e Å-³.

16

Compounds S8 and L8 were obtained as a mixture, for more details, see Supporting Information.

17

Crystal Structure Data for Compound S5 CCDC, 8152756, C18H20N2O2, MW = 296.36; monoclinic; space group Cc, a = 17.6508 (17), b = 10.4452 (10), c = 18.9547 (18) Å, α = 90.00˚, β = 117.458 (2)˚, γ = 90.00˚, V = 3100.9 (5)ų, T = 298 (2) K, Z = 8, D C = 1.270 Mg/m³, µ = 0.084 mm-¹, λ = 0.71073 Å, F(000) = 1264: crystal size 0.16 × 0.12 × 0.10 mm³; 4566 independent reflections [R(int) = 0.0467], reflections collected 9790, refinement method: full-matrix least-squares on F²: goodness-of-fit on F² 1.014; final R indices [I > 2σ(I)], R1 = 0.0704, wR2 = 0.1641, largest diff. peak and hole 0.389 Å-³ and
-0.233 e Å-³.