Rhodium-Catalyzed Asymmetric Addition of Organoboronic Acids to Aldimines Using Chiral Spiro Monophosphite-Olefin Ligands: Method Development and Mechanistic Studies.
Shan, Huanyu; Zhou, Qiaoxia; Yu, Jinglu; Zhang, Shuoqing; Hong, Xin; Lin, Xufeng; The Journal of organic chemistry 83 (2018) 11873–11885; doi:10.1021/acs.joc.8b01764

data_4035177
_publ_section_title
;
 Rhodium-Catalyzed Asymmetric Addition of Organoboronic Acids to Aldimines
 Using Chiral Spiro Monophosphite-Olefin Ligands: Method Development and
 Mechanistic Studies.
;
_journal_issue                   19
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              11873
_journal_page_last               11885
_journal_paper_doi               10.1021/acs.joc.8b01764
_journal_volume                  83
_journal_year                    2018
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C45 H64 O6'
_chemical_formula_sum            'C45 H64 O6'
_chemical_formula_weight         700.96
_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
_atom_sites_solution_primary     direct
_audit_creation_date             2017-07-24
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
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_cell_length_b                   16.17984(19)
_cell_length_c                   24.4076(3)
_cell_measurement_reflns_used    12544
_cell_measurement_temperature    170
_cell_measurement_theta_max      66.7892
_cell_measurement_theta_min      3.2744
_cell_volume                     4160.61(9)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
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_diffrn_detector_area_resol_mean 10.3592
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_details
;
  1 omega   15.00  113.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       41.5688   38.0000 -150.0000 98

  2 omega  -25.00   67.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       41.5688  -38.0000   30.0000 92

  3 omega    3.00   92.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       41.5688 -125.0000  -30.0000 89

  4 omega   31.00   78.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -91.0000  -79.0000 47

  5 omega   35.00   65.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -93.0000 -141.0000 30

  6 omega   90.00  133.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -93.0000 -141.0000 43

  7 omega    9.00  128.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -90.0000   50.0000 119

  8 omega   32.00  168.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   15.0000  -60.0000 136

  9 omega  112.00  166.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   45.0000  -30.0000 54

 10 omega   52.00   77.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -45.0000 -180.0000 25

 11 omega   19.00   74.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -45.0000   30.0000 55

 12 omega   19.00   56.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -45.0000  -30.0000 37

 13 omega   23.00   74.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -45.0000  -90.0000 51

 14 omega   96.00  124.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -91.0000  -79.0000 28

 15 omega   86.00  123.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -90.0000  132.0000 37

 16 omega   19.00   75.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -45.0000  120.0000 56

 17 omega   16.00   65.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -90.0000  132.0000 49
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0927340000
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_diffrn_orient_matrix_UB_22      -0.0516412000
_diffrn_orient_matrix_UB_23      0.0511285000
_diffrn_orient_matrix_UB_31      -0.1082362000
_diffrn_orient_matrix_UB_32      0.0604616000
_diffrn_orient_matrix_UB_33      0.0139689000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0563
_diffrn_reflns_av_unetI/netI     0.0402
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
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_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            27682
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        66.900
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_diffrn_reflns_theta_min         3.277
_diffrn_source                   'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.568
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69514
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
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_exptl_crystal_colour            colourless
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_exptl_crystal_density_diffrn    1.119
_exptl_crystal_description       block
_exptl_crystal_F_000             1528
_exptl_crystal_size_max          0.49
_exptl_crystal_size_mid          0.46
_exptl_crystal_size_min          0.4
_refine_diff_density_max         0.217
_refine_diff_density_min         -0.252
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Flack x determined using 2640 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.13(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     472
_refine_ls_number_reflns         7314
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_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0512
_refine_ls_R_factor_gt           0.0454
_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^)+(0.0708P)^2^+0.2367P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
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_refine_ls_wR_factor_ref         0.1169
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_reflns_number_gt                6680
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_cod_data_source_file            jo8b01764_si_003.cif
_cod_data_source_block           170722_shy_20170714_2
_cod_database_code               4035177
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'c h o'
_shelx_estimated_absorpt_t_max   0.805
_shelx_estimated_absorpt_t_min   0.768
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_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:
 C19(H19), C20(H20), C23(H23), C25(H25), C35(H35), C36(H36), C39(H39), C41(H41)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C10(H10A,H10B), C21(H21A,H21B), C22(H22A,H22B), C24(H24A,H24B),
 C37(H37A,H37B), C38(H38A,H38B), C40(H40A,H40B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C14(H14), C17(H17)
2.d Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C),
 C45(H45A,H45B,H45C)
;
_shelx_res_checksum              63200
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_olex2_submission_special_instructions 'No special instructions were received'