Highly efficient desymmetrization of cyclopropenes to azabicyclo[3.1.0]hexanes with five continuous stereogenic centers by copper-catalyzed [3 + 2] cycloadditions
Yuan, Yang; Zheng, Zhan-Jiang; Ye, Fei; Ma, Jun-Han; Xu, Zheng; Bai, Xing-Feng; Li, Li; Xu, Li-Wen; Organic Chemistry Frontiers 5 (2018) 2759–; doi:10.1039/C8QO00761F

data_1554406
_publ_section_title
;
 Highly efficient desymmetrization of cyclopropenes to
 azabicyclo[3.1.0]hexanes with five continuous stereogenic centers by
 copper-catalyzed [3 + 2] cycloadditions
;
_journal_issue                   18
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              2759
_journal_paper_doi               10.1039/C8QO00761F
_journal_volume                  5
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C30 H31 Br N2 O3'
_chemical_formula_sum            'C30 H31 Br N2 O3'
_chemical_formula_weight         547.47
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-02-02
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.12.08 svn.r3473 for OlexSys, GUI svn.r5457)
;
_audit_update_record
;
2018-02-03 deposited with the CCDC.
2018-08-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.298(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.248(2)
_cell_length_b                   7.6262(12)
_cell_length_c                   27.213(4)
_cell_measurement_reflns_used    2580
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      21.812
_cell_measurement_theta_min      2.776
_cell_volume                     2727.1(7)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      296.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0358
_diffrn_reflns_av_unetI/netI     0.1189
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            16627
_diffrn_reflns_point_group_measured_fraction_full 0.918
_diffrn_reflns_point_group_measured_fraction_max 0.860
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.624
_diffrn_reflns_theta_min         1.550
_exptl_absorpt_coefficient_mu    1.540
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6479
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/3 (Bruker,2014/3) was used for absorption correction. wR2(int) was 0.0711 before and 0.0622 after correction. The Ratio of minimum to maximum transmission is 0.8690. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.333
_exptl_crystal_description       block
_exptl_crystal_F_000             1136
_refine_diff_density_max         0.428
_refine_diff_density_min         -0.374
_refine_diff_density_rms         0.077
_refine_ls_abs_structure_details
;
 Flack x determined using 1772 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.054(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     655
_refine_ls_number_reflns         10898
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.1405
_refine_ls_R_factor_gt           0.0694
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0917P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1790
_refine_ls_wR_factor_ref         0.2167
_reflns_Friedel_coverage         0.637
_reflns_Friedel_fraction_full    0.825
_reflns_Friedel_fraction_max     0.724
_reflns_number_gt                5809
_reflns_number_total             10898
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8qo00761f2.cif
_cod_data_source_block           180130yy_0m
_cod_database_code               1554406
_shelx_shelxl_version_number     2014/7
_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.a Ternary CH refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14), C41(H41), C42(H42), C43(H43), C44(H44)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C9(H9A,H9B), C37(H37A,H37B), C39(H39A,H39B)
2.c Aromatic/amide H refined with riding coordinates:
 N2(H2), C2(H2A), C3(H3), C16(H16), C17(H17), C19(H19), C20(H20), C22(H22),
 C23(H23), C24(H24), C25(H25), C26(H26), C29(H29), C30(H30), N4(H4), C32(H32),
 C33(H33), C46(H46), C47(H47), C49(H49), C50(H50), C52(H52), C53(H53), C54(H54),
  C55(H55), C56(H56), C59(H59), C60(H60)
2.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C10(H10A,H10B,H10C), C28(H28A,H28B,H28C), C38(H38A,H38B,
 H38C), C40(H40A,H40B,H40C), C58(H58A,H58B,H58C)
;
_shelx_res_checksum              50421
_shelx_hkl_checksum              80209
_olex2_submission_special_instructions 'No special instructions were received'