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_1569921
_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_formula_moiety         'C25 H17 F6 N O3 S'
_chemical_formula_sum            'C25 H17 F6 N O3 S'
_chemical_formula_weight         525.46
_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                   8.0066(3)
_cell_length_b                   14.4740(6)
_cell_length_c                   19.8606(8)
_cell_measurement_reflns_used    9998
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      28.29
_cell_measurement_theta_min      2.49
_cell_volume                     2301.60(16)
_computing_cell_refinement       'SAINT V8.40B'
_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 1.000
_diffrn_measured_fraction_theta_max 0.999
_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  0.0279
_diffrn_reflns_av_unetI/netI     0.0264
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            19572
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.298
_diffrn_reflns_theta_min         2.051
_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    0.218
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6863
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0594 before and 0.0469 after correction.
The Ratio of minimum to maximum transmission is 0.9203.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.516
_exptl_crystal_description       block
_exptl_crystal_F_000             1072
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.246
_refine_diff_density_min         -0.304
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 2235 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(2)
_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     325
_refine_ls_number_reflns         5707
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0324
_refine_ls_R_factor_gt           0.0298
_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^)+(0.0343P)^2^+0.6029P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0700
_refine_ls_wR_factor_ref         0.0717
_reflns_Friedel_coverage         0.763
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                5398
_reflns_number_total             5707
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04581a2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 1569919--1569921.cif.'
_cod_database_code               1569921
_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
2.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C17(H17A,H17B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C12(H12), C13(H13), C14(H14),
 C15(H15), C19(H19), C21(H21), C23(H23)
;
_olex2_submission_special_instructions 'No special instructions were received'
_shelx_estimated_absorpt_t_min   0.958
_shelx_estimated_absorpt_t_max   0.966
_olex2_diffrn_ambient_temperature_device 'Oxford Cryostream 800'
_shelx_res_checksum              32965