Synthesis and Application of Hexamethyl-1,1'-spirobiindane-Based Phosphine-Oxazoline Ligands in Ni-Catalyzed Asymmetric Arylation of Cyclic Aldimines.
Sun, Weiye; Gu, Haorui; Lin, Xufeng; The Journal of organic chemistry 83 (2018) 4034–4043; doi:10.1021/acs.joc.8b00422

data_4035496
_publ_section_title
;
 Synthesis and Application of Hexamethyl-1,1'-spirobiindane-Based
 Phosphine-Oxazoline Ligands in Ni-Catalyzed Asymmetric Arylation of
 Cyclic Aldimines.
;
_journal_issue                   7
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              4034
_journal_page_last               4043
_journal_paper_doi               10.1021/acs.joc.8b00422
_journal_volume                  83
_journal_year                    2018
_chemical_absolute_configuration rmad
_chemical_formula_moiety         '2(C50 H48 N O P), C6 H14 O'
_chemical_formula_sum            'C106 H110 N2 O3 P2'
_chemical_formula_weight         1521.89
_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             2017-10-13
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.631(3)
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   11.6873(3)
_cell_length_b                   15.3134(3)
_cell_length_c                   14.6013(4)
_cell_measurement_reflns_used    18390
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      66.6609
_cell_measurement_theta_min      3.2314
_cell_volume                     2445.64(11)
_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
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_reduction
;
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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_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
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_diffrn_detector_area_resol_mean 10.3592
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_diffrn_measured_fraction_theta_max 0.993
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;
  1 omega   14.00   96.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       41.5636 -125.0000 -180.0000 82

  2 omega   17.00  111.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       41.5636   38.0000  -60.0000 94

  3 omega   23.00  109.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       41.5636   38.0000   30.0000 86

  4 omega   68.00  106.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   45.0000    0.0000 38

  5 omega   27.00   76.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -45.0000  -30.0000 49

  6 omega   94.00  177.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   15.0000 -150.0000 83

  7 omega   68.00  166.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   45.0000   60.0000 98

  8 omega   20.00  116.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -77.0000 -180.0000 96

  9 omega  140.00  172.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000    0.0000 32

 10 omega   20.00   77.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -45.0000   30.0000 57

 11 omega    7.00  137.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000    0.0000   30.0000 130

 12 omega   37.00   63.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -77.0000   90.0000 26

 13 omega   84.00  111.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -77.0000   90.0000 27

 14 omega   67.00  107.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000    0.0000 40

 15 omega   36.00   72.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -45.0000 -150.0000 36

 16 omega  121.00  168.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   45.0000    0.0000 47

 17 omega   19.00   71.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -45.0000   90.0000 52

 18 omega  -99.00  -18.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.5636  125.0000  -60.0000 81

 19 omega    8.00  120.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       41.5636   77.0000  150.0000 112

 20 omega    8.00  120.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       41.5636   77.0000   60.0000 112

 21 omega -161.00  -50.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -76.0000  158.0000 111

 22 omega -162.00  -49.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000   90.0000 113

 23 omega   63.00  168.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   63.0000 -137.0000 105

 24 omega    8.00  131.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -89.0000   71.0000 123

 25 omega   63.00  168.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   63.0000  -85.0000 105

 26 omega   60.00  172.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000  -60.0000 112

 27 omega   66.00  168.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   45.0000  150.0000 102

 28 omega    8.00  132.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -91.0000  -65.0000 124

 29 omega   19.00   77.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -45.0000  -90.0000 58

 30 omega    8.00  120.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       41.5636   77.0000  -90.0000 112

 31 omega    8.00  120.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       41.5636   77.0000    0.0000 112

 32 omega   11.00  116.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       41.5636   63.0000 -137.0000 105

 33 omega -162.00  -49.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -78.0000   22.0000 113
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0796392000
_diffrn_orient_matrix_UB_12      -0.0665423000
_diffrn_orient_matrix_UB_13      0.0744498000
_diffrn_orient_matrix_UB_21      -0.1136126000
_diffrn_orient_matrix_UB_22      -0.0322111000
_diffrn_orient_matrix_UB_23      0.0202957000
_diffrn_orient_matrix_UB_31      -0.0239068000
_diffrn_orient_matrix_UB_32      -0.0682266000
_diffrn_orient_matrix_UB_33      -0.0822397000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0523
_diffrn_reflns_av_unetI/netI     0.0257
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            41724
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        66.771
_diffrn_reflns_theta_max         66.771
_diffrn_reflns_theta_min         4.194
_diffrn_source                   'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.761
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.34633
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
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.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.033
_exptl_crystal_description       block
_exptl_crystal_F_000             814
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.46
_exptl_crystal_size_min          0.36
_refine_diff_density_max         0.447
_refine_diff_density_min         -0.239
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 3374 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     551
_refine_ls_number_reflns         8562
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0637
_refine_ls_R_factor_gt           0.0585
_refine_ls_shift/su_max          0.063
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1127P)^2^+0.2275P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
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_refine_ls_wR_factor_ref         0.1623
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_reflns_Friedel_fraction_max     0.978
_reflns_number_gt                7792
_reflns_number_total             8562
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b00422_si_002.cif
_cod_data_source_block           171012_swy_l7
_cod_original_cell_volume        2445.63(10)
_cod_database_code               4035496
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'c h n o p'
_shelx_estimated_absorpt_t_max   0.771
_shelx_estimated_absorpt_t_min   0.711
_reflns_odcompleteness_completeness 99.98
_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. Restrained distances
 C56-C54 = C55-C54
 1.53 with sigma of 0.02
 C56-C55
 2.53 with sigma of 0.04
3. Others
 Fixed Sof: O2(0.5) C51(0.5) H51A(0.5) H51B(0.5) H51C(0.5) C52(0.5) H52(0.5)
 C53(0.5) H53A(0.5) H53B(0.5) H53C(0.5) C54(0.5) H54(0.5) C55(0.5) H55A(0.5)
 H55B(0.5) H55C(0.5) C56(0.5) H56A(0.5) H56B(0.5) H56C(0.5)
4.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C52(H52), C54(H54)
4.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C13(H13A,H13B)
4.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C7(H7), C18(H18), C20(H20), C22(H22), C23(H23), C24(H24), C25(H25),
 C26(H26), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C40(H40), C41(H41),
  C42(H42), C43(H43), C44(H44), C46(H46), C47(H47), C48(H48), C49(H49), C50(H50)
4.d Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,
 H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C51(H51A,H51B,H51C), C53(H53A,
 H53B,H53C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C)
;
_shelx_res_checksum              67374
_shelx_hkl_checksum              57388
_olex2_submission_special_instructions 'No special instructions were received'