Copper-Catalyzed Asymmetric Radical 1,2-Carboalkynylation of Alkenes with Alkyl Halides and Terminal Alkynes.
Dong, Xiao-Yang; Cheng, Jiang-Tao; Zhang, Yu-Feng; Li, Zhong-Liang; Zhan, Tian-Ya; Chen, Ji-Jun; Wang, Fu-Li; Yang, Ning-Yuan; Ye, Liu; Gu, Qiang-Shuai; Liu, Xin-Yuan; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c03130

data_4134911
_publ_section_title
;
 Copper-Catalyzed Asymmetric Radical 1,2-Carboalkynylation of Alkenes with
 Alkyl Halides and Terminal Alkynes.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c03130
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C29 H32 O3'
_chemical_formula_sum            'C29 H32 O3'
_chemical_formula_weight         428.54
_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             2019-10-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.8373(3)
_cell_length_b                   8.5386(5)
_cell_length_c                   47.775(3)
_cell_measurement_reflns_used    9665
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.24
_cell_measurement_theta_min      3.70
_cell_volume                     2381.2(2)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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      100
_diffrn_detector                 'Bruker PHOTON 100 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker CMOS area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0380
_diffrn_reflns_av_unetI/netI     0.0192
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       57
_diffrn_reflns_limit_l_min       -57
_diffrn_reflns_number            37780
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.242
_diffrn_reflns_theta_min         3.701
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.595
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.7014
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0771 before and 0.0680 after correction. The Ratio of minimum to maximum transmission is 0.9314. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.195
_exptl_crystal_description       block
_exptl_crystal_F_000             920
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.35
_refine_diff_density_max         0.165
_refine_diff_density_min         -0.127
_refine_diff_density_rms         0.026
_refine_ls_abs_structure_details
;
 Flack x determined using 1750 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(5)
_refine_ls_extinction_coef       0.0112(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     296
_refine_ls_number_reflns         4333
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0254
_refine_ls_R_factor_gt           0.0253
_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^)+(0.0273P)^2^+0.5368P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0639
_refine_ls_wR_factor_ref         0.0640
_reflns_Friedel_coverage         0.691
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                4303
_reflns_number_total             4333
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c03130_si_002.cif
_cod_data_source_block           cxy0961_0m
_cod_database_code               4134911
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.819
_shelx_estimated_absorpt_t_min   0.788
_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 Ternary CH refined with riding coordinates:
 C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B)
2.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C15(H15), C14(H14), C11(H11), C16(H16), C17(H17), C19(H19), C20(H20),
 C21(H21), C22(H22), C23(H23)
2.d Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C13(H13A,H13B,H13C), C24(H24A,H24B,H24C), C28(H28A,H28B,
 H28C), C29(H29A,H29B,H29C), C25(H25A,H25B,H25C)
;
_olex2_submission_special_instructions 'No special instructions were received'