Stereoselective Synthesis of Pentasubstituted 1,3-Dienes via Ni-Catalyzed Reductive Coupling of Unsymmetrical Internal Alkynes
Zhou, Zhijun; Chen, Jiachang; chen, Herong; Kong, Wangqing; Chemical Science  (2020) –; doi:10.1039/D0SC04173D

data_1559060
_publ_section_title
;
 Stereoselective Synthesis of Pentasubstituted 1,3-Dienes via Ni-Catalyzed
 Reductive Coupling of Unsymmetrical Internal Alkynes
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC04173D
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C34 H30 O6'
_chemical_formula_sum            'C34 H30 O6'
_chemical_formula_weight         534.58
_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   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-05-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-08-13 deposited with the CCDC.	2020-09-10 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 92.008(9)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   6.6786(13)
_cell_length_b                   19.494(4)
_cell_length_c                   21.437(4)
_cell_measurement_reflns_used    617
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      38.79
_cell_measurement_theta_min      3.06
_cell_volume                     2789.2(9)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XH (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.972
_diffrn_measured_fraction_theta_max 0.972
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.2470
_diffrn_reflns_av_unetI/netI     0.2148
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            7810
_diffrn_reflns_theta_full        50.40
_diffrn_reflns_theta_max         50.40
_diffrn_reflns_theta_min         2.06
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.703
_exptl_absorpt_correction_T_max  0.7500
_exptl_absorpt_correction_T_min  0.4201
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.273
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1128
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.215
_refine_diff_density_min         -0.215
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.3(8)
_refine_ls_extinction_coef       0.0075(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   0.944
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     678
_refine_ls_number_reflns         4964
_refine_ls_number_restraints     166
_refine_ls_restrained_S_all      0.941
_refine_ls_R_factor_all          0.2052
_refine_ls_R_factor_gt           0.0967
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1212P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2063
_refine_ls_wR_factor_ref         0.2695
_reflns_number_gt                1912
_reflns_number_total             4964
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d0sc04173d2.cif
_cod_data_source_block           cu_190514b_0m
_cod_database_code               1559060
_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. Restrained distances
 C19A-C17A = C20A-C19A = C21A-C20A
 1.51 with sigma of 0.01
 C1-C5 = C4-C5 = C3-C4 = C3-C2 = C2-C1
 1.51 with sigma of 0.01
 C21A-C20A = C21A-C16A
 1.51 with sigma of 0.02
 C18-C19 = C20-C19 = C21-C20 = C21-C17 = C17-C18
 1.51 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C21A) \\sim Ueq, Uanis(C26A) \\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(C2A)
\\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C33A) \\sim Ueq, Uanis(C32A) \\sim Ueq,
Uanis(C11A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C13) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21)
\\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq,
Uanis(C31) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C25)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C24) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C6A)
\\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C27) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
4.a Ternary CH refined with riding coordinates:
 C8(H8), C11(H11), C12(H12), C13(H13), C8A(H8A), C11A(H11A), C12A(H12A),
 C13A(H13A)
4.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C7(H7A,H7B), C20(H20A,H20B), C21(H21A,H21B),
 C2A(H2AA,H2AB), C3A(H3AA,H3AB), C7A(H7AA,H7AB), C19A(H19A,H19B), C20A(H20C,
 H20D)
4.c Aromatic/amide H refined with riding coordinates:
 C28(H28), C27(H27), C26(H26), C25(H25), C24(H24), C30(H30), C31(H31),
 C32(H32), C33(H33), C34(H34), C23A(H23A), C24A(H24A), C25A(H25A), C26A(H26A),
 C27A(H27A), C29A(H29A), C30A(H30A), C31A(H31A), C32A(H32A), C33A(H33A)
4.d Fitted hexagon refined as free rotating group:
 C23(C28,C27,C26,C25,C24), C29(C30,C31,C32,C33,C34), C22A(C23A,C24A,C25A,C26A,
 C27A), C28A(C29A,C30A,C31A,C32A,C33A)
4.e Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C22(H22A,H22B,H22C), C6A(H6AA,H6AB,H6AC), C34A(H34A,H34B,H34C)
;
_olex2_submission_special_instructions 'No special instructions were received'