Synthesis and application of a new chiral monodentate spiro phosphoramidite ligand based on hexamethyl-1,1'-spirobiindane backbone in asymmetric hydroamination/arylation of alkenes.
Shan, Huanyu; Pan, Rihuang; Lin, Xufeng; Organic & biomolecular chemistry 16 (2018) 6183–6186; doi:10.1039/c8ob01785a

data_7156372
_publ_section_title
;
 Synthesis and application of a new chiral monodentate spiro
 phosphoramidite ligand based on hexamethyl-1,1'-spirobiindane backbone in
 asymmetric hydroamination/arylation of alkenes.
;
_journal_issue                   34
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              6183
_journal_page_last               6186
_journal_paper_doi               10.1039/c8ob01785a
_journal_volume                  16
_journal_year                    2018
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C23 H28 O2, C6 H14 O'
_chemical_formula_sum            'C29 H42 O3'
_chemical_formula_weight         438.63
_chemical_name_common            '(R)-6, 6?-HMSIOL'
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-01-07
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_audit_update_record
;
2018-07-23 deposited with the CCDC.
2018-08-13 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 104.616(4)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   10.8110(4)
_cell_length_b                   11.3987(3)
_cell_length_c                   11.7982(4)
_cell_measurement_reflns_used    4305
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      67.2475
_cell_measurement_theta_min      3.8688
_cell_volume                     1406.86(8)
_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
;
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)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293.15
_diffrn_detector_area_resol_mean 10.3592
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1094580000
_diffrn_orient_matrix_UB_12      0.0547831000
_diffrn_orient_matrix_UB_13      0.0947911000
_diffrn_orient_matrix_UB_21      -0.0767755000
_diffrn_orient_matrix_UB_22      -0.0200570000
_diffrn_orient_matrix_UB_23      0.0919467000
_diffrn_orient_matrix_UB_31      0.0617643000
_diffrn_orient_matrix_UB_32      -0.1219777000
_diffrn_orient_matrix_UB_33      0.0273761000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0322
_diffrn_reflns_av_unetI/netI     0.0286
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            10334
_diffrn_reflns_theta_full        67.36
_diffrn_reflns_theta_max         67.36
_diffrn_reflns_theta_min         3.87
_diffrn_source                   'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.504
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68445
_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    1.035
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             480
_exptl_crystal_size_max          0.49
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.36
_refine_diff_density_max         0.248
_refine_diff_density_min         -0.157
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details 'Flack (1983), 2281 Friedel pairs'
_refine_ls_abs_structure_Flack   0.4(3)
_refine_ls_extinction_coef       0.0109(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     305
_refine_ls_number_reflns         4921
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0563
_refine_ls_R_factor_gt           0.0466
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0777P)^2^+0.0922P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1240
_refine_ls_wR_factor_ref         0.1356
_reflns_number_gt                4155
_reflns_number_total             4921
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c8ob01785a2.cif
_cod_data_source_block           160107_shy20160105
_cod_depositor_comments          'Adding full bibliography for 7156372.cif.'
_cod_original_cell_volume        1406.84(8)
_cod_database_code               7156372
_chemical_oxdiff_formula         'c10 h19 n2 o8'
_reflns_odcompleteness_completeness 99.92
_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, All O(H) groups
2. Restrained distances
 H1-O1
 0.86 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C25(H25), C27(H27)
3.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C13(H13A,H13B)
3.c Aromatic/amide H refined with riding coordinates:
 C1(H1A), C4(H4), C17(H17), C20(H20)
3.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C26(H26A,
 H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C)
3.e Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;