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_1559059
_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 ad
_chemical_formula_moiety         'C40 H36 N4 O7, C H Cl3'
_chemical_formula_sum            'C41 H37 Cl3 N4 O7'
_chemical_formula_weight         804.09
_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
_audit_creation_date             2019-12-09
_audit_creation_method
; 
Olex2 1.2 
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506) 
;
_audit_update_record
;
2020-06-11 deposited with the CCDC.	2020-09-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.339(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.3144(9)
_cell_length_b                   9.8595(7)
_cell_length_c                   14.5355(10)
_cell_measurement_reflns_used    9809
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      30.51
_cell_measurement_theta_min      2.50
_cell_volume                     1899.8(2)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       'Bruker APEX2'
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      296(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.946
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0362
_diffrn_reflns_av_unetI/netI     0.0301
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.946
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            33634
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.922
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.692
_diffrn_reflns_theta_min         1.536
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.298
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.5746
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS-2008/1 (Bruker,2008)'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.406
_exptl_crystal_description       block
_exptl_crystal_F_000             836
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.361
_refine_diff_density_min         -0.708
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
; 
 Flack x determined using 3895 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   -0.03(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     525
_refine_ls_number_reflns         10874
_refine_ls_number_restraints     31
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0776
_refine_ls_R_factor_gt           0.0644
_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^)+(0.1266P)^2^+0.5452P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1816
_refine_ls_wR_factor_ref         0.2025
_reflns_Friedel_coverage         0.852
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.896
_reflns_number_gt                9196
_reflns_number_total             10874
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc04173d2.cif
_cod_data_source_block           mo_191205a_0m
_cod_database_code               1559059
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.957
_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, All O(H) groups 
2. Restrained distances 
 Cl3-C41 = Cl3A-C41A = Cl1-C41 = Cl2-C41 = Cl2A-C41A = Cl1A-C41A 
 1.73 with sigma of 0.01 
 Cl2A-Cl3A 
 2.92 with sigma of 0.04 
 Cl3A-Cl1A 
 2.92 with sigma of 0.04 
 Cl2A-Cl1A 
 2.92 with sigma of 0.04 
 Cl3-Cl1 
 2.92 with sigma of 0.04 
 Cl1-Cl2 
 2.92 with sigma of 0.04 
 Cl2-Cl3 
 2.92 with sigma of 0.04 
 C41-Cl1 \\sim C41A-Cl1A 
 with sigma of 0.02 
 C41-Cl2 \\sim C41A-Cl2A 
 with sigma of 0.02 
 C41-Cl3 \\sim C41A-Cl3A 
 with sigma of 0.02 
 Cl1-Cl2 \\sim Cl1A-Cl2A 
 with sigma of 0.04 
 Cl1-Cl3 \\sim Cl1A-Cl3A 
 with sigma of 0.04 
 Cl2-Cl3 \\sim Cl2A-Cl3A 
 with sigma of 0.04 
3. Uiso/Uaniso restraints and constraints 
Uanis(Cl3) \\sim Ueq, Uanis(Cl3A) \\sim Ueq: with sigma of 0.01 and sigma for 
terminal atoms of 0.02 
Uanis(Cl3) = Uanis(Cl2A) 
Uanis(C41) = Uanis(C41A) 
4. Others 
 Sof(C41A)=Sof(H41A)=Sof(Cl1A)=Sof(Cl2A)=Sof(Cl3A)=1-FVAR(1) 
 Sof(C41)=Sof(H41)=Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=FVAR(1) 
5.a Ternary CH refined with riding coordinates: 
 C9(H9), C41(H41), C41A(H41A) 
5.b Secondary CH2 refined with riding coordinates: 
 C10(H10A,H10B), C13(H13A,H13B), C14(H14A,H14B), C29(H29A,H29B), C31(H31A, 
 H31B), C32(H32A,H32B) 
5.c Aromatic/amide H refined with riding coordinates: 
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C19(H19), C20(H20), C22(H22), 
 C23(H23), C35(H35), C36(H36), C38(H38), C39(H39) 
5.d Idealised Me refined as rotating group: 
 C16(H16A,H16B,H16C), C33(H33A,H33B,H33C), C40(H40A,H40B,H40C) 
5.e Idealised tetrahedral OH refined as rotating group: 
 O5(H5A) 
;
_shelx_res_checksum              62655
_olex2_submission_special_instructions 'No special instructions were received'