Asymmetric Synthesis of Dibenzo[b,d]azepines by Cu-Catalyzed Reductive or Borylative Cyclization
Rodríguez-Salamanca, Patricia; Martín de la Calle , Rocío; Rodríguez, Veronica; Merino, Pedro; Fernández, Rosario; Lassaletta, Jose M.; Hornillos, Valentín; Chemical Science  (2021) –; doi:10.1039/D1SC04980A

data_1565182
_publ_section_title
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 Asymmetric Synthesis of Dibenzo[b,d]azepines by Cu-Catalyzed Reductive or
 Borylative Cyclization
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC04980A
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C H2 Cl2, 2(C27 H30 B N O2)'
_chemical_formula_sum            'C55 H62 B2 Cl2 N2 O4'
_chemical_formula_weight         907.58
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-06-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-07-09 deposited with the CCDC.	2021-11-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.171(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.4051(10)
_cell_length_b                   21.314(2)
_cell_length_c                   11.3738(12)
_cell_measurement_reflns_used    9821
_cell_measurement_temperature    193.0
_cell_measurement_theta_max      26.34
_cell_measurement_theta_min      2.65
_cell_volume                     2456.1(4)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      193.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0658
_diffrn_reflns_av_unetI/netI     0.0620
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            47449
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.391
_diffrn_reflns_theta_min         2.010
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.180
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5363
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1435 before and 0.0863 after correction.
The Ratio of minimum to maximum transmission is 0.7195.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.227
_exptl_crystal_description       block
_exptl_crystal_F_000             964
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CH2Cl2 - Pentane'
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.47
_exptl_crystal_size_min          0.23
_refine_diff_density_max         0.528
_refine_diff_density_min         -0.418
_refine_diff_density_rms         0.087
_refine_ls_abs_structure_details
;
 Flack x determined using 4259 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     612
_refine_ls_number_reflns         10028
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0568
_refine_ls_R_factor_gt           0.0531
_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^)+(0.0730P)^2^+0.6246P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1278
_refine_ls_wR_factor_ref         0.1319
_reflns_Friedel_coverage         0.943
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                9405
_reflns_number_total             10028
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04980a2.cif
_cod_data_source_block           vh0221a_0m
_cod_original_cell_volume        2456.0(4)
_cod_database_code               1565182
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.960
_shelx_estimated_absorpt_t_min   0.915
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 Cl2A, C55
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
Cl2A \\sim C55: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 1.7A
4. Others
 Sof(HB)=Sof(HC)=Sof(Cl2A)=1-FVAR(1)
 Sof(H)=Sof(HA)=Sof(Cl2)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C5(HE), C6(HF), C32(H32), C33(H33)
5.b Secondary CH2 refined with riding coordinates:
 C55(H,HA), C55(HB,HC), C21(HT,HU), C48(H48A,H48B)
5.c Aromatic/amide H refined with riding coordinates:
 C7(HG), C8(HH), C9(HI), C10(HJ), C11(HK), C12(HL), C13(HM), C14(HN), C16(HO),
 C17(HP), C18(HQ), C19(HR), C20(HS), C34(H34), C35(H35), C36(H36), C37(H37),
 C38(H38), C39(H39), C40(H40), C41(H41), C43(H43), C44(H44), C45(H45), C46(H46),
  C47(H47)
5.d Idealised Me refined as rotating group:
 C24(HV,HW,HX), C25(HY,HZ,H1), C26(H3,H4,H5), C27(H6,H7,H8), C51(H51A,H51B,
 H51C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C)
;
_shelx_res_checksum              98662
_shelx_hkl_checksum              22898
_olex2_submission_special_instructions 'No special instructions were received'