Highly Selective and Catalytic Generation of Acyclic Quaternary Carbon Stereocenters via Functionalization of 1,3-Dienes with CO<sub>2</sub>.
Chen, Xiao-Wang; Zhu, Lei; Gui, Yong-Yuan; Jing, Ke; Jiang, Yuan-Xu; Bo, Zhi-Yu; Lan, Yu; Li, Jing; Yu, Da-Gang; Journal of the American Chemical Society 141 (2019) 18825–18835; doi:10.1021/jacs.9b09721

data_4129169
_publ_section_title
;
 Highly Selective and Catalytic Generation of Acyclic Quaternary Carbon
 Stereocenters via Functionalization of 1,3-Dienes with CO<sub>2</sub>.
;
_journal_issue                   47
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              18825
_journal_page_last               18835
_journal_paper_doi               10.1021/jacs.9b09721
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H23 Br O2'
_chemical_formula_sum            'C25 H23 Br O2'
_chemical_formula_weight         435.34
_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             2019-03-12
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.0516(17)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.40748(19)
_cell_length_b                   18.4667(4)
_cell_length_c                   11.24341(19)
_cell_measurement_reflns_used    8072
_cell_measurement_temperature    295.9(3)
_cell_measurement_theta_max      72.4910
_cell_measurement_theta_min      4.3150
_cell_volume                     2120.82(7)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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_environment      air
_diffrn_ambient_temperature      295.9(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_details
;
  1 omega  -31.00   53.00   1.0000    3.5700
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -57.0000  -30.0000 84

  2 omega  -31.00   53.00   1.0000    3.5700
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -57.0000   90.0000 84

  3 omega   10.00  104.00   1.0000    3.5700
omega____ theta____ kappa____ phi______ frames
    -       36.5421   77.0000 -150.0000 94

  4 omega    7.00  108.00   1.0000    3.5700
omega____ theta____ kappa____ phi______ frames
    -       36.5421   19.0000   30.0000 101

  5 omega   23.00   90.00   1.0000    3.5700
omega____ theta____ kappa____ phi______ frames
    -       36.5421 -125.0000   30.0000 67

  6 omega  -31.00   53.00   1.0000    3.5700
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -57.0000 -150.0000 84

  7 omega    1.00   75.00   1.0000    3.5700
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -99.0000   90.0000 74

  8 omega    1.00   75.00   1.0000    3.5700
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -99.0000 -120.0000 74

  9 omega   10.00  104.00   1.0000    3.5700
omega____ theta____ kappa____ phi______ frames
    -       36.5421   77.0000   90.0000 94

 10 omega   10.00  104.00   1.0000    3.5700
omega____ theta____ kappa____ phi______ frames
    -       36.5421   77.0000  -90.0000 94

 11 omega   39.00  109.00   1.0000   14.2600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -180.0000 70

 12 omega   38.00   91.00   1.0000   14.2600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -30.0000 53

 13 omega   38.00   91.00   1.0000   14.2600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -150.0000 53

 14 omega   39.00  109.00   1.0000   14.2600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   30.0000 70

 15 omega   38.00   91.00   1.0000   14.2600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  150.0000 53

 16 omega  100.00  178.00   1.0000   14.2600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000   30.0000 78

 17 omega   40.00   98.00   1.0000   14.2600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000    0.0000 58

 18 omega   37.00  146.00   1.0000   14.2600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -15.0000 -120.0000 109

 19 omega   39.00  109.00   1.0000   14.2600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  120.0000 70

 20 omega   38.00   91.00   1.0000   14.2600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  120.0000 53

 21 omega   38.00   91.00   1.0000   14.2600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   60.0000 53

 22 omega   40.00   98.00   1.0000   14.2600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -90.0000 58

 23 omega   39.00  109.00   1.0000   14.2600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -150.0000 70

 24 omega   90.00  175.00   1.0000   14.2600
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000 -120.0000 85

 25 omega   40.00   98.00   1.0000   14.2600
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  150.0000 58

 26 omega   91.00  176.00   1.0000   14.2600
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000  -60.0000 85

 27 omega   38.00  116.00   1.0000   14.2600
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  -30.0000 78

 28 omega   20.00  104.00   1.0000    3.5700
omega____ theta____ kappa____ phi______ frames
    -       36.5421   57.0000 -180.0000 84

 29 omega  -33.00   -8.00   1.0000    3.5700
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -38.0000 -120.0000 25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0179127000
_diffrn_orient_matrix_UB_12      0.0455494000
_diffrn_orient_matrix_UB_13      -0.1104261000
_diffrn_orient_matrix_UB_21      0.0129934000
_diffrn_orient_matrix_UB_22      0.0689685000
_diffrn_orient_matrix_UB_23      0.0785475000
_diffrn_orient_matrix_UB_31      0.1491935000
_diffrn_orient_matrix_UB_32      -0.0114214000
_diffrn_orient_matrix_UB_33      0.0334034000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0409
_diffrn_reflns_av_unetI/netI     0.0343
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            21248
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.831
_diffrn_reflns_theta_min         4.668
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.767
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57465
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.363
_exptl_crystal_description       irregular
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.338
_refine_diff_density_min         -0.300
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 2908 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.016(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     509
_refine_ls_number_reflns         8242
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0553
_refine_ls_R_factor_gt           0.0501
_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^)+(0.0907P)^2^+0.0871P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1394
_refine_ls_wR_factor_ref         0.1481
_reflns_Friedel_coverage         0.912
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                7119
_reflns_number_total             8242
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b09721_si_002.cif
_cod_data_source_block           ydg-cxw01
_cod_depositor_comments
'Adding full bibliography for 4129169--4129170.cif.'
_cod_database_code               4129169
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C00M(H00A,H00B), C013(H01I,H01J)
2.b Aromatic/amide H refined with riding coordinates:
 C008(H008), C00F(H00F), C00H(H00H), C00K(H00K), C00L(H00L), C00O(H00O),
 C00P(H00P), C00Q(H00Q), C00R(H00R), C00S(H00S), C00T(H00T), C00U(H00U),
 C00V(H00V), C00W(H00W), C00X(H00X), C00Y(H00Y), C010(H010), C011(H011),
 C012(H012), C014(H014), C015(H015), C016(H016), C017(H017), C018(H018),
 C019(H019), C01A(H01K), C01B(H01L), C01C(H01M), C01G(H01G), C01H(H01H)
2.c Idealised Me refined as rotating group:
 C01F(H01A,H01B,H01C), C01I(H01N,H01O,H01P), C01J(H01Q,H01R,H01S), C01K(H01D,
 H01E,H01F)
;
_shelx_res_checksum              54817
_shelx_hkl_checksum              61072
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2019-03-12
_olex2_submission_special_instructions 'No special instructions were received'