Z-Selective Dienylation Enables Stereodivergent Construction of Dienes and Unravels a Ligand-Driven Mechanistic Dichotomy
Dang, Hang T.; Nguyen, Viet D.; Haug, Graham C.; Vuong, Ngan T. H.; Arman, Hadi D.; Larionov, Oleg V.; ACS Catalysis  (2021) 1042–1052; doi:10.1021/acscatal.0c05574

data_4518462
_publ_section_title
;
 Z-Selective Dienylation Enables Stereodivergent Construction of Dienes
 and Unravels a Ligand-Driven Mechanistic Dichotomy
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              1042
_journal_page_last               1052
_journal_paper_doi               10.1021/acscatal.0c05574
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C36 H51 Br O2'
_chemical_formula_sum            'C36 H51 Br O2'
_chemical_formula_weight         595.67
_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
_audit_creation_date             2020-08-01
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6143)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.7810(4)
_cell_length_b                   9.7023(5)
_cell_length_c                   56.176(3)
_cell_measurement_reflns_used    7794
_cell_measurement_temperature    98(2)
_cell_measurement_theta_max      26.5380
_cell_measurement_theta_min      2.1760
_cell_volume                     3150.9(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28e (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28e (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28e (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      98(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -35.00  82.00   0.50   25.00    --   -7.60  50.00 -92.00  234
  2  \w    -85.00  26.00   0.50   25.00    --    4.20 -38.00 -90.00  222
  3  \w    -97.00  17.00   0.50   25.00    --   -7.60 -38.00 -60.00  228
  4  \w    -32.00  77.00   0.50   25.00    --   -7.60  38.00  60.00  218
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RCD3): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0686082000
_diffrn_orient_matrix_UB_12      0.0432212000
_diffrn_orient_matrix_UB_13      0.0073418000
_diffrn_orient_matrix_UB_21      0.0770866000
_diffrn_orient_matrix_UB_22      0.0114042000
_diffrn_orient_matrix_UB_23      -0.0096217000
_diffrn_orient_matrix_UB_31      -0.0663395000
_diffrn_orient_matrix_UB_32      0.0578756000
_diffrn_orient_matrix_UB_33      -0.0035792000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0823
_diffrn_reflns_av_unetI/netI     0.0537
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       66
_diffrn_reflns_limit_l_min       -66
_diffrn_reflns_number            39426
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.048
_diffrn_reflns_theta_max         25.048
_diffrn_reflns_theta_min         2.130
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.334
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60062
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28e (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.256
_exptl_crystal_description       plate
_exptl_crystal_F_000             1272
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.323
_refine_diff_density_min         -0.534
_refine_diff_density_rms         0.072
_refine_ls_abs_structure_details
;
 Flack x determined using 1781 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.003(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     358
_refine_ls_number_reflns         5567
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0601
_refine_ls_R_factor_gt           0.0546
_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^)+(0.0400P)^2^+6.5000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1188
_refine_ls_wR_factor_ref         0.1226
_reflns_Friedel_coverage         0.700
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                5177
_reflns_number_total             5567
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c05574_si_005.cif
_cod_data_source_block           cd1801b
_cod_original_cell_volume        3150.8(3)
_cod_database_code               4518462
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         Br1O5C40H20
_chemical_oxdiff_usercomment     'brominated steriod'
_shelx_estimated_absorpt_t_max   0.912
_shelx_estimated_absorpt_t_min   0.638
_reflns_odcompleteness_completeness 99.79
_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 Ternary CH refined with riding coordinates:
 C1(H1), C7(H7), C14(H14), C6(H6), C10(H10), C28(H28), C25(H25), C29(H29)
2.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C13(H13A,H13B), C2(H2A,H2B), C16(H16A,H16B), C12(H12A,H12B),
 C5(H5A,H5B), C32(H32A,H32B), C8(H8A,H8B), C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C23(H23), C21(H21), C24(H24), C20(H20), C26(H26), C27(H27), C4(H4)
2.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C34(H34A,H34B,H34C), C30(H30A,H30B,
 H30C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C)
;
_shelx_res_checksum              51978
_shelx_hkl_checksum              95614
_olex2_exptl_crystal_mounting_method 'nylnon loop'
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.339
_oxdiff_exptl_absorpt_empirical_full_min 0.790