Benign catalysis with zinc: atom-economical and divergent synthesis of nitrogen heterocycles by formal [3 + 2] annulation of isoxazoles with ynol ethers
Zhu, Xin-Qi; Yuan, Han; Sun, Qing; Zhou, Bo; Han, Xiao-Qin; Zhang, Zhi-Xin; Lu, Xin; Ye, Long-Wu; Green Chemistry 20 (2018) 4287–; doi:10.1039/C8GC02051E

data_7231395
_publ_section_title
;
 Benign catalysis with zinc: atom-economical and divergent synthesis of
 nitrogen heterocycles by formal [3 + 2] annulation of isoxazoles with
 ynol ethers
;
_journal_issue                   18
_journal_name_full               'Green Chemistry'
_journal_page_first              4287
_journal_paper_doi               10.1039/C8GC02051E
_journal_volume                  20
_journal_year                    2018
_chemical_formula_moiety         '5(C15 H17 N O2), C15 H16 N O2'
_chemical_formula_sum            'C90 H101 N6 O12'
_chemical_formula_weight         1458.76
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-02-22
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_audit_update_record
;
2018-01-26 deposited with the CCDC.
2018-08-20 downloaded from the CCDC.
;
_cell_angle_alpha                106.471(3)
_cell_angle_beta                 107.031(3)
_cell_angle_gamma                108.096(3)
_cell_formula_units_Z            4
_cell_length_a                   19.911(3)
_cell_length_b                   20.945(3)
_cell_length_c                   23.811(4)
_cell_measurement_reflns_used    8308
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      24.12
_cell_measurement_theta_min      2.29
_cell_volume                     8223(2)
_computing_cell_refinement       'Bruker SMART'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      173.15
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.967
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0364
_diffrn_reflns_av_unetI/netI     0.0828
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            71114
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         0.982
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.078
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.178
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3116
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: ethyl acetate and hexane'
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.8
_exptl_crystal_size_min          0.6
_refine_diff_density_max         0.369
_refine_diff_density_min         -0.199
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1981
_refine_ls_number_reflns         36450
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.1043
_refine_ls_R_factor_gt           0.0635
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0741P)^2^+1.0319P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1576
_refine_ls_wR_factor_ref         0.1816
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22745
_reflns_number_total             36450
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8gc02051e2.cif
_cod_data_source_block           y0215m
_cod_depositor_comments          'Adding full bibliography for 7231395.cif.'
_cod_database_code               7231395
_shelxl_version_number           2013-2
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
: with sigma of 0.01 and sigma for terminal atoms of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C125(H12a,H12b), C35(H35a,H35b), C95(H95a,H95b), C5(H5a,H5b), C65(H65a,H65b),
 C20(H20a,H20b), C170(H17d,H17e), C50(H50a,H50b), C80(H80a,H80b), C110(H11g,
 H11h)
3.b Aromatic/amide H refined with riding coordinates:
 N10(H10d), N12(H12), N8(H8), N3(H3), N11(H11i), N2(H2), N7(H7), N5(H5),
 N9(H9), N6(H6), N1(H1), N4(H4), C100(H100), C29(H29), C175(H175), C115(H115),
 C130(H130), C134(H134), C145(H145), C119(H119), C104(H104), C176(H176),
 C179(H179), C10(H10), C40(H40), C55(H55), C101(H101), C149(H149), C74(H74),
 C44(H44), C25(H25), C42(H42), C102(H102), C28(H28), C89(H89), C177(H177),
 C133(H133), C26(H26), C132(H132), C85(H85), C147(H147), C59(H59), C103(H103),
 C131(H131), C41(H41), C118(H118), C27(H27), C146(H146), C116(H116), C164(H164),
  C160(H160), C57(H57), C148(H148), C178(H178), C56(H56), C73(H73), C86(H86),
 C117(H117), C11(H11), C43(H43), C72(H72), C87(H87), C70(H70), C162(H162),
 C14(H14), C12(H12l), C58(H58), C88(H88), C163(H163), C71(H71), C13(H13),
 C161(H161), C155(H155), C140(H140)
3.c Idealised Me refined as rotating group:
 C120(H12i,H12j,H12k), C150(H15j,H15k,H15l), C173(H17a,H17b,H17c), C128(H12c,
 H12d,H12e), C45(H45a,H45b,H45c), C105(H10a,H10b,H10c), C126(H12f,H12g,H12h),
 C113(H11a,H11b,H11c), C165(H16a,H16b,H16c), C135(H13a,H13b,H13c), C143(H14a,
 H14b,H14c), C83(H83a,H83b,H83c), C68(H68a,H68b,H68c), C180(H18a,H18b,H18c),
 C60(H60a,H60b,H60c), C90(H90a,H90b,H90c), C23(H23a,H23b,H23c), C30(H30a,H30b,
 H30c), C96(H96a,H96b,H96c), C66(H66a,H66b,H66c), C15(H15a,H15b,H15c),
 C156(H15d,H15e,H15f), C75(H75a,H75b,H75c), C98(H98a,H98b,H98c), C38(H38a,H38b,
 H38c), C36(H36a,H36b,H36c), C51(H51a,H51b,H51c), C81(H81a,H81b,H81c),
 C111(H11d,H11e,H11f), C8(H8a,H8b,H8c), C6(H6a,H6b,H6c), C158(H15g,H15h,H15i),
 C141(H14d,H14e,H14f), C171(H17f,H17g,H17h), C21(H21a,H21b,H21c), C53(H53a,H53b,
 H53c)
;
_olex2_submission_special_instructions 'No special instructions were received'