Diastereoselective synthesis of benzazocines by Zn(OTf)<sub>2</sub>-catalyzed (4+4) cyclocondensation of multisubstituted donor-acceptor cyclopropanes with anthranils.
Huang, Xuelian; Yang, Gaosheng; Chai, Zhuo; Chemical communications (Cambridge, England) 61 (2025) 3704–3707; doi:10.1039/d4cc06690a

data_7134222
_publ_section_title
;
 Diastereoselective synthesis of benzazocines by
 Zn(OTf)<sub>2</sub>-catalyzed (4+4) cyclocondensation of multisubstituted
 donor-acceptor cyclopropanes with anthranils.
;
_journal_issue                   18
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              3704
_journal_page_last               3707
_journal_paper_doi               10.1039/d4cc06690a
_journal_volume                  61
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C35 H31 Br O5'
_chemical_formula_sum            'C35 H31 Br O5'
_chemical_formula_weight         611.51
_space_group_crystal_system      trigonal
_space_group_IT_number           152
_space_group_name_Hall           'P 31 2"'
_space_group_name_H-M_alt        'P 31 2 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-03-29
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-04-18 deposited with the CCDC.	2025-02-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   11.5209(2)
_cell_length_b                   11.5209(2)
_cell_length_c                   40.4128(12)
_cell_measurement_reflns_used    9626
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      65.400
_cell_measurement_theta_min      4.431
_cell_volume                     4645.39(18)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.968
_diffrn_measured_fraction_theta_max 0.964
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0938
_diffrn_reflns_av_unetI/netI     0.0333
_diffrn_reflns_Laue_measured_fraction_full 0.968
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            104615
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.387
_diffrn_reflns_theta_min         4.431
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.129
_exptl_absorpt_correction_T_max  0.7530
_exptl_absorpt_correction_T_min  0.3499
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1562 before and 0.1081 after correction.
The Ratio of minimum to maximum transmission is 0.4647.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.312
_exptl_crystal_description       block
_exptl_crystal_F_000             1896
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.703
_refine_diff_density_min         -0.780
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 1796 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.080(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     427
_refine_ls_number_reflns         5495
_refine_ls_number_restraints     231
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0651
_refine_ls_R_factor_gt           0.0550
_refine_ls_shift/su_max          0.000
_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^+2.6817P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1437
_refine_ls_wR_factor_ref         0.1533
_reflns_Friedel_coverage         0.734
_reflns_Friedel_fraction_full    0.976
_reflns_Friedel_fraction_max     0.970
_reflns_number_gt                4743
_reflns_number_total             5495
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc06690a2.cif
_cod_data_source_block           1_a
_cod_depositor_comments
'Adding full bibliography for 7134221--7134226.cif.'
_cod_original_cell_volume        4645.4(2)
_cod_database_code               7134222
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.675
_shelx_estimated_absorpt_t_min   0.652
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C4-C5 \\sim C4-C5A
 with sigma of 0.02
 C5-C10 \\sim C5A-C10A
 with sigma of 0.02
 C5-C6 \\sim C5A-C6A
 with sigma of 0.02
 C10-C9 \\sim C10A-C9A
 with sigma of 0.02
 C6-C7 \\sim C6A-C7A
 with sigma of 0.02
 C8-C7 \\sim C8A-C7A
 with sigma of 0.02
 C8-C9 \\sim C8A-C9A
 with sigma of 0.02
 C4-C10 \\sim C4-C10A
 with sigma of 0.04
 C4-C6 \\sim C4-C6A
 with sigma of 0.04
 C5-C7 \\sim C5A-C7A
 with sigma of 0.04
 C5-C9 \\sim C5A-C9A
 with sigma of 0.04
 C10-C6 \\sim C10A-C6A
 with sigma of 0.04
 C10-C8 \\sim C10A-C8A
 with sigma of 0.04
 C6-C8 \\sim C6A-C8A
 with sigma of 0.04
 C7-C9 \\sim C7A-C9A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C5 \\sim C10 \\sim C6 \\sim C8 \\sim C7 \\sim C9: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
C5A \\sim C10A \\sim C6A \\sim C8A \\sim C7A \\sim C9A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C5) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C8) \\sim
Ueq, Uanis(C7) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C5A) \\sim Ueq,
Uanis(C10A) \\sim Ueq, Uanis(C6A) \\sim Ueq, Uanis(C8A) \\sim Ueq, Uanis(C7A)
\\sim Ueq, Uanis(C9A) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
4. Rigid body (RIGU) restrains
 C5, C10, C6, C8, C7, C9
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C5A, C10A, C6A, C8A, C7A, C9A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Others
 Sof(C5A)=Sof(C10A)=Sof(H10A)=Sof(C6A)=Sof(H6A)=Sof(C8A)=Sof(H8A)=Sof(C7A)=
 Sof(H7A)=Sof(C9A)=Sof(H9A)=1-FVAR(1)
 Sof(C5)=Sof(C10)=Sof(H10)=Sof(C6)=Sof(H6)=Sof(C8)=Sof(H8)=Sof(C7)=Sof(H7)=
 Sof(C9)=Sof(H9)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C19(H19), C17(H17), C2(H2), C28(H28)
6.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B)
6.c Aromatic/amide H refined with riding coordinates:
 C31(H31), C12(H12), C15(H15), C16(H16), C22(H22), C33(H33), C32(H32),
 C24(H24), C13(H13), C26(H26), C35(H35), C23(H23), C34(H34), C10(H10), C6(H6),
 C8(H8), C25(H25), C7(H7), C9(H9), C10A(H10A), C6A(H6A), C8A(H8A), C7A(H7A),
 C9A(H9A)
6.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C29(H29A,H29B,H29C)
;
_shelx_res_checksum              91471
_shelx_hkl_checksum              94504
_olex2_submission_special_instructions 'No special instructions were received'