Chemodivergence in Pd-catalyzed desymmetrization of allenes: enantioselective [4+3] cycloaddition, desymmetric allenylic substitution and enynylation.
Luo, Pengfei; Li, Long; Mao, Xinfang; Sun, Zheng; Wang, Yingcheng; Peng, Fangzhi; Shao, Zhihui; Chemical science 14 (2023) 10812–10823; doi:10.1039/d3sc04581a

data_1569919
_publ_section_title
;
 Chemodivergence in Pd-catalyzed desymmetrization of allenes:
 enantioselective [4+3] cycloaddition, desymmetric allenylic substitution
 and enynylation.
;
_journal_issue                   39
_journal_name_full               'Chemical science'
_journal_page_first              10812
_journal_page_last               10823
_journal_paper_doi               10.1039/d3sc04581a
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H24 Br2 N2 O2 S'
_chemical_formula_sum            'C26 H24 Br2 N2 O2 S'
_chemical_formula_weight         588.35
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-10-13
_audit_creation_method
;
FinalCif V88 by Daniel Kratzert, Freiburg 2022,
https://github.com/dkratzert/FinalCif
;
_audit_update_record
;
2023-03-25 deposited with the CCDC.	2023-09-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.8154(7)
_cell_length_b                   17.400(2)
_cell_length_c                   23.776(3)
_cell_measurement_reflns_used    5317
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      28.23
_cell_measurement_theta_min      2.49
_cell_volume                     2405.8(5)
_computing_cell_refinement       'SAINT V8.40B'
_computing_data_collection
'Bruker BIS V6.2.16/2021-10-22 && APEX4 2022.1-1'
_computing_data_reduction        'SAINT V8.40B'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00
_diffrn_detector                 CPAD
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'Bruker PHOTON'
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE dual wavelength Mo/Cu'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0477
_diffrn_reflns_av_unetI/netI     0.0728
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            5619
_diffrn_reflns_point_group_measured_fraction_full 0.951
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.277
_diffrn_reflns_theta_min         2.075
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.483
_exptl_absorpt_correction_T_max  0.745686
_exptl_absorpt_correction_T_min  0.450138
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.1212 before and 0.0762 after correction.
 The Ratio of minimum to maximum transmission is 0.60.

Final HKLF 4 output contains 23430 reflections, Rint = 0.0811
 (7917 with I > 3sig(I), Rint = 0.0590)
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.624
_exptl_crystal_description       block
_exptl_crystal_F_000             1184
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.877
_refine_diff_density_min         -0.611
_refine_diff_density_rms         0.118
_refine_ls_abs_structure_details
;
 Flack x determined using 1531 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.044(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     301
_refine_ls_number_reflns         5619
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0661
_refine_ls_R_factor_gt           0.0472
_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^)+(0.0644P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1101
_refine_ls_wR_factor_ref         0.1185
_reflns_Friedel_coverage         0.665
_reflns_Friedel_fraction_full    0.899
_reflns_Friedel_fraction_max     0.884
_reflns_number_gt                4599
_reflns_number_total             5619
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04581a2.cif
_cod_data_source_block           4
_cod_depositor_comments
'Adding full bibliography for 1569919--1569921.cif.'
_cod_original_cell_volume        2405.9(5)
_cod_database_code               1569919
_shelx_shelxl_version_number     2018/3
_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 Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C18(H18A,H18B)
2.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C3(H3), C7(H7), C11(H11), C14(H14), C20(H20), C22(H22), C23(H23),
 C24(H24), C25(H25), C26(H26)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_shelx_estimated_absorpt_t_min   0.543
_shelx_estimated_absorpt_t_max   0.606
_olex2_diffrn_ambient_temperature_device 'Oxford Cryostream 800'
_shelx_res_checksum              31095