Synthesis and application of a new hexamethyl-1,1'-spirobiindane-based chiral bisphosphine (HMSI-PHOS) ligand in asymmetric allylic alkylation.
Chang, Shirui; Wang, Lei; Lin, Xufeng; Organic & biomolecular chemistry 16 (2018) 2239–2247; doi:10.1039/c8ob00279g

data_1549028
_publ_section_title
;
 Synthesis and application of a new hexamethyl-1,1'-spirobiindane-based
 chiral bisphosphine (HMSI-PHOS) ligand in asymmetric allylic alkylation.
;
_journal_issue                   13
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2239
_journal_page_last               2247
_journal_paper_doi               10.1039/c8ob00279g
_journal_volume                  16
_journal_year                    2018
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C23 H26 Br2 O2'
_chemical_formula_sum            'C23 H26 Br2 O2'
_chemical_formula_weight         494.26
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-04-14
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_audit_update_record
;
2018-01-31 deposited with the CCDC.
2018-03-06 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   7.5979(5)
_cell_length_b                   14.0001(10)
_cell_length_c                   19.6290(12)
_cell_measurement_reflns_used    3862
_cell_measurement_temperature    170.8
_cell_measurement_theta_max      29.5498
_cell_measurement_theta_min      3.0834
_cell_volume                     2088.0(2)
_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)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      170.8
_diffrn_detector_area_resol_mean 10.3592
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0179598000
_diffrn_orient_matrix_UB_12      0.0475459000
_diffrn_orient_matrix_UB_13      -0.0100985000
_diffrn_orient_matrix_UB_21      -0.0304194000
_diffrn_orient_matrix_UB_22      0.0167934000
_diffrn_orient_matrix_UB_23      0.0320763000
_diffrn_orient_matrix_UB_31      0.0864719000
_diffrn_orient_matrix_UB_32      -0.0039274000
_diffrn_orient_matrix_UB_33      0.0133370000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0485
_diffrn_reflns_av_unetI/netI     0.0490
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            12839
_diffrn_reflns_theta_full        25.35
_diffrn_reflns_theta_max         25.35
_diffrn_reflns_theta_min         3.09
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.898
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75608
_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    1.572
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.29
_exptl_crystal_size_min          0.23
_refine_diff_density_max         0.313
_refine_diff_density_min         -0.561
_refine_diff_density_rms         0.077
_refine_ls_abs_structure_details 'Flack (1983), 1615 Friedel pairs'
_refine_ls_abs_structure_Flack   -0.004(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     252
_refine_ls_number_reflns         3806
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.0443
_refine_ls_R_factor_gt           0.0354
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0420P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0781
_refine_ls_wR_factor_ref         0.0832
_reflns_number_gt                3335
_reflns_number_total             3806
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c8ob00279g2.cif
_cod_data_source_block           160413_m6_db_oh
_cod_depositor_comments          'Adding full bibliography for 1549028.cif.'
_cod_database_code               1549028
_chemical_oxdiff_formula         'c10 h10 n2 o8 Br1'
_reflns_odcompleteness_completeness 99.35
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.a Secondary CH2 refined with riding coordinates:
 C8(H8a,H8b), C10(H10a,H10b)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C17(H17)
2.c Idealised Me refined as rotating group:
 C18(H18a,H18b,H18c), C19(H19a,H19b,H19c), C20(H20a,H20b,H20c), C21(H21a,H21b,
 H21c), C22(H22a,H22b,H22c), C23(H23a,H23b,H23c)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2)
;