Palladium-Catalyzed Amide-Directed Enantioselective Carboboration of Unactivated Alkenes Using a Chiral Monodentate Oxazoline Ligand
Bai, Zibo; Zheng, Sujuan; Bai, Ziqian; Song, Fangfang; Wang, Hao; Peng, Qian; Chen, Gong; He, Gang; ACS Catalysis 9 (2019) 6502–; doi:10.1021/acscatal.9b01350

data_4514803
_publ_section_title
;
 Palladium-Catalyzed Amide-Directed Enantioselective Carboboration of
 Unactivated Alkenes Using a Chiral Monodentate Oxazoline Ligand
;
_journal_issue                   7
_journal_name_full               'ACS Catalysis'
_journal_page_first              6502
_journal_paper_doi               10.1021/acscatal.9b01350
_journal_volume                  9
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C30 H36 B N3 O3'
_chemical_formula_sum            'C30 H36 B N3 O3'
_chemical_formula_weight         497.43
_space_group_crystal_system      tetragonal
_space_group_IT_number           92
_space_group_name_Hall           'P 4abw 2nw'
_space_group_name_H-M_alt        'P 41 21 2'
_symmetry_space_group_name_Hall  'P 4abw 2nw'
_symmetry_space_group_name_H-M   'P 41 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-20
_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            8
_cell_length_a                   9.03220(10)
_cell_length_b                   9.03220(10)
_cell_length_c                   68.9818(6)
_cell_measurement_reflns_used    23223
_cell_measurement_temperature    294.15
_cell_measurement_theta_max      78.4420
_cell_measurement_theta_min      4.9680
_cell_volume                     5627.58(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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      294.15
_diffrn_detector                 PILT
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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    -84.00  92.70   0.38    1.01    --    5.00  -9.00-122.00  465
  2  \w   -140.00  38.22   0.38    1.01    --  -50.10  -9.00-122.00  469
  3  \w   -135.00-109.92   0.38    4.04    -- -110.00   9.00  53.00   66
  4  \w   -151.00-110.34   0.38    4.04    -- -110.00  -9.00-122.00  107
  5  \w    -67.00  38.26   0.38    1.01    --  -50.10  38.00-180.00  277
  6  \w    -54.00 -19.80   0.38    1.01    --  -50.10 -66.00 136.05   90
  7  \w    -96.00 -22.28   0.38    1.01    --  -50.10 -44.00  25.98  194
  8  \w   -186.00-129.76   0.38    4.04    -- -110.00 -59.00  53.12  148
  9  \w   -119.00 -92.78   0.38    4.04    -- -110.00  72.00 150.00   69
 10  \w   -177.00 -82.00   0.38    4.04    -- -110.00 -43.00-121.60  250
 11  \w   -136.00 -22.00   0.38    4.04    -- -110.00  72.00-180.00  300
 12  \w   -175.00-148.78   0.38    4.04    -- -110.00 -57.00-180.00   69
 13  \w   -122.00 -95.78   0.38    4.04    -- -110.00 -57.00-180.00   69
 14  \w   -138.00 -62.76   0.38    4.04    -- -110.00  72.00-156.75  198
 15  \w   -123.00 -93.36   0.38    4.04    -- -110.00 -59.00  53.12   78
 16  \w   -132.00 -21.80   0.38    4.04    -- -110.00  38.00  30.00  290
;
_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      0.0173524000
_diffrn_orient_matrix_UB_12      0.1588491000
_diffrn_orient_matrix_UB_13      -0.0077916000
_diffrn_orient_matrix_UB_21      -0.0102342000
_diffrn_orient_matrix_UB_22      -0.0588640000
_diffrn_orient_matrix_UB_23      -0.0209209000
_diffrn_orient_matrix_UB_31      -0.1693980000
_diffrn_orient_matrix_UB_32      0.0197848000
_diffrn_orient_matrix_UB_33      0.0004669000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0354
_diffrn_reflns_av_unetI/netI     0.0182
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       83
_diffrn_reflns_limit_l_min       -87
_diffrn_reflns_number            43274
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.686
_diffrn_reflns_theta_min         4.938
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.596
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.28947
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.174
_exptl_crystal_description       plate
_exptl_crystal_F_000             2128
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.198
_refine_diff_density_min         -0.264
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 1898 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     417
_refine_ls_number_reflns         6066
_refine_ls_number_restraints     136
_refine_ls_restrained_S_all      1.160
_refine_ls_R_factor_all          0.0617
_refine_ls_R_factor_gt           0.0584
_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^)+(0.0913P)^2^+0.9994P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1624
_refine_ls_wR_factor_ref         0.1657
_reflns_Friedel_coverage         0.632
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.979
_reflns_number_gt                5567
_reflns_number_total             6066
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b01350_si_003.cif
_cod_data_source_block           p20190319b
_cod_original_cell_volume        5627.58(13)
_cod_database_code               4514803
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C30H36BN3O3
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.860
_reflns_odcompleteness_completeness 99.53
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C25-C26 = C25A-C26A
 1.54 with sigma of 0.01
 O2-C25 = O2A-C25A = O3-C26 = O3A-C26A
 1.45 with sigma of 0.01
 C25-C27 = C25-C28 = C26-C29 = C26-C30
 1.54 with sigma of 0.01
 C25A-C27A = C25A-C28A = C26A-C29A = C26A-C30A
 1.54 with sigma of 0.01
 C26-C27 = C26-C28 = C25-C29 = C25-C30 = C27-C28 = C29-C30
 2.52 with sigma of 0.01
 C26A-C27A = C26A-C28A = C25A-C29A = C25A-C30A = C27A-C28A = C29A-C30A
 2.52 with sigma of 0.01
 B1-O2 \\sim B1-O3 \\sim B1-O2A \\sim B1-O3A
 with sigma of 0.01
 B1-C25 \\sim B1-C25A \\sim B1-C26 \\sim B1-C26A
 with sigma of 0.01
3. Restrained planarity
 C12, B1, O2, O3
 with sigma of 0.01
 C12, B1, O2A, O3A
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C27) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30)
\\sim Ueq, Uanis(C27A) \\sim Ueq, Uanis(C28A) \\sim Ueq, Uanis(C29A) \\sim Ueq,
Uanis(C30A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.02
Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(O3)
\\sim Ueq, Uanis(C25A) \\sim Ueq, Uanis(C26A) \\sim Ueq, Uanis(O2A) \\sim Ueq,
Uanis(O3A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.02
5. Others
 Sof(O2A)=Sof(O3A)=Sof(C25A)=Sof(C26A)=Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=
 Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29A)=Sof(H29D)=Sof(H29E)=
 Sof(H29F)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(1)
 Sof(O2)=Sof(O3)=Sof(C25)=Sof(C26)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C12(H12), C13(H13)
6.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C14(H14A,H14B)
6.c Aromatic/amide H refined with riding coordinates:
 N2(H2), C1(H1), C2(H2A), C3(H3), C7(H7), C8(H8), C9(H9), C17(H17), C20(H20),
 C21(H21), C22(H22), C23(H23)
6.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C24(H24A,H24B,H24C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C27A(H27D,H27E,H27F),
 C28A(H28D,H28E,H28F), C29A(H29D,H29E,H29F), C30A(H30D,H30E,H30F)
;
_shelx_res_checksum              34099
_shelx_hkl_checksum              8787
_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 2.620
_oxdiff_exptl_absorpt_empirical_full_min 0.516