Copper-catalyzed propargylic C-H functionalization for allene syntheses.
Zhang, Dongjie; Fan, Junjie; Shi, Yaqi; Huang, Yankai; Fu, Chunling; Wu, Xiaoyan; Ma, Shengming; Chemical science 14 (2023) 9191–9196; doi:10.1039/d3sc01501g

data_1569660
_publ_section_title
;
 Copper-catalyzed propargylic C-H functionalization for allene syntheses.
;
_journal_issue                   34
_journal_name_full               'Chemical science'
_journal_page_first              9191
_journal_page_last               9196
_journal_paper_doi               10.1039/d3sc01501g
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H27 Br N2 O2 S'
_chemical_formula_sum            'C20 H27 Br N2 O2 S'
_chemical_formula_weight         439.40
_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             2022-05-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-05-15 deposited with the CCDC.	2023-08-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.530(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.3288(2)
_cell_length_b                   22.8188(8)
_cell_length_c                   10.9506(3)
_cell_measurement_reflns_used    4938
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      29.3614
_cell_measurement_theta_min      1.8560
_cell_volume                     2081.11(11)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_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      293(2)
_diffrn_detector_area_resol_mean 10.3592
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.886
_diffrn_measurement_details
;
  1 omega  -72.00   11.00   1.0000   18.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.4683  -38.0000  150.0000 83

  2 omega  -38.00   64.00   1.0000   18.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.4683   38.0000  -30.0000 102

  3 omega  -20.00   69.00   1.0000   18.0000
omega____ theta____ kappa____ phi______ frames
    -       11.7808   77.0000   90.0000 89
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0564317000
_diffrn_orient_matrix_UB_12      -0.0155299000
_diffrn_orient_matrix_UB_13      0.0357358000
_diffrn_orient_matrix_UB_21      -0.0612485000
_diffrn_orient_matrix_UB_22      0.0196381000
_diffrn_orient_matrix_UB_23      -0.0191619000
_diffrn_orient_matrix_UB_31      -0.0177110000
_diffrn_orient_matrix_UB_32      -0.0184339000
_diffrn_orient_matrix_UB_33      -0.0505159000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0346
_diffrn_reflns_av_unetI/netI     0.0651
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.886
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            15814
_diffrn_reflns_point_group_measured_fraction_full 0.935
_diffrn_reflns_point_group_measured_fraction_max 0.786
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.426
_diffrn_reflns_theta_min         1.860
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.092
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81082
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.402
_exptl_crystal_F_000             912
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.26
_refine_diff_density_max         0.499
_refine_diff_density_min         -0.458
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 1933 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.007(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.011
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     473
_refine_ls_number_reflns         9055
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.0912
_refine_ls_R_factor_gt           0.0488
_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^)+(0.0443P)^2^+0.1100P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0948
_refine_ls_wR_factor_ref         0.1120
_reflns_Friedel_coverage         0.733
_reflns_Friedel_fraction_full    0.867
_reflns_Friedel_fraction_max     0.681
_reflns_number_gt                5914
_reflns_number_total             9055
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01501g2.cif
_cod_data_source_block           220506_zdj_4_094
_cod_depositor_comments          'Adding full bibliography for 1569660.cif.'
_cod_database_code               1569660
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'c h n o s br'
_shelx_estimated_absorpt_t_max   0.612
_shelx_estimated_absorpt_t_min   0.453
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C15(H15A,H15B), C16(H16A,H16B),
 C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C29(H29A,H29B), C30(H30A,H30B),
  C31(H31A,H31B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C38(H38A,
 H38B), C39(H39A,H39B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C13(H13), C21(H21), C22(H22), C24(H24),
 C25(H25), C33(H33)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C20(H20A,H20B,H20C), C27(H27A,H27B,H27C), C40(H40A,H40B,H40C)
;
_shelx_res_checksum              8056
_olex2_submission_special_instructions 'No special instructions were received'