Umpolung Reactivity of in Situ Generated Phosphido-Boranes: An Entry to P-Stereogenic Aminophosphine-Boranes.
Lemouzy, Sébastien; Membrat, Romain; Olivieri, Enzo; Jean, Marion; Albalat, Muriel; Nuel, Didier; Giordano, Laurent; Hérault, Damien; Buono, Gérard; The Journal of organic chemistry 84 (2019) 4551–4557; doi:10.1021/acs.joc.9b00333

data_4034267
_publ_section_title
;
 Umpolung Reactivity of in Situ Generated Phosphido-Boranes: An Entry to
 P-Stereogenic Aminophosphine-Boranes.
;
_journal_issue                   7
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              4551
_journal_page_last               4557
_journal_paper_doi               10.1021/acs.joc.9b00333
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H25 B N P'
_chemical_formula_sum            'C17 H25 B N P'
_chemical_formula_weight         285.16
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-03-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3461 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.05511(5)
_cell_length_b                   11.64625(8)
_cell_length_c                   18.10204(10)
_cell_measurement_reflns_used    19679
_cell_measurement_temperature    293
_cell_measurement_theta_max      70.8560
_cell_measurement_theta_min      4.4600
_cell_volume                     1698.185(18)
_computing_cell_refinement       'CrysAlisPro 1.171.39.44a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.44a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.44a (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      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3048
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_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     17.00 115.00   1.00    1.00    --   41.07  38.00 120.00   98
  2  \w     51.00 124.00   1.00    1.00    --   41.07-171.00-117.00   73
  3  \w      1.00  82.00   1.00    1.00    --   41.07 -99.00 150.00   81
  4  \w     76.00 174.00   1.00    1.00    --  101.41  45.00  30.00   98
  5  \w     69.00 178.00   1.00    1.00    --  101.41  77.00 150.00  109
  6  \w     94.00 175.00   1.00    1.00    --  101.41 125.00-180.00   81
  7  \w     94.00 175.00   1.00    1.00    --  101.41 125.00 120.00   81
  8  \w     69.00 178.00   1.00    1.00    --  101.41  77.00-180.00  109
  9  \w   -113.00 -13.00   1.00    1.00    --  -41.07 -57.00 -90.00  100
 10  \w   -117.00  -8.00   1.00    1.00    --  -41.07 -77.00-180.00  109
 11  \w     69.00 178.00   1.00    1.00    --  101.41  77.00 -60.00  109
 12  \w     69.00 178.00   1.00    1.00    --  101.41  77.00-120.00  109
 13  \w     28.00 121.00   1.00    1.00    --  101.41-125.00 -90.00   93
 14  \w     94.00 175.00   1.00    1.00    --  101.41 125.00  60.00   81
 15  \w   -117.00  -8.00   1.00    1.00    --  -41.07 -77.00  30.00  109
 16  \w     15.00  91.00   1.00    1.00    --   41.07-115.00  24.00   76
 17  \w     72.00 174.00   1.00    1.00    --  101.41  61.00  90.00  102
 18  \w     94.00 175.00   1.00    1.00    --  101.41 125.00 -90.00   81
 19  \w     69.00 178.00   1.00    1.00    --  101.41  77.00  30.00  109
 20  \w     69.00 178.00   1.00    1.00    --  101.41  77.00 -30.00  109
 21  \w   -117.00  -8.00   1.00    1.00    --  -41.07 -77.00  90.00  109
 22  \w   -117.00  -8.00   1.00    1.00    --  -41.07 -77.00 -90.00  109
 23  \w     72.00 174.00   1.00    1.00    --  101.41  61.00 120.00  102
 24  \w     69.00 178.00   1.00    1.00    --  101.41  77.00-150.00  109
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0661050000
_diffrn_orient_matrix_UB_12      0.0379455000
_diffrn_orient_matrix_UB_13      -0.0760281000
_diffrn_orient_matrix_UB_21      -0.1766167000
_diffrn_orient_matrix_UB_22      0.0086135000
_diffrn_orient_matrix_UB_23      0.0321625000
_diffrn_orient_matrix_UB_31      0.0319296000
_diffrn_orient_matrix_UB_32      0.1264337000
_diffrn_orient_matrix_UB_33      0.0206480000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0296
_diffrn_reflns_av_unetI/netI     0.0137
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            24726
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.962
_diffrn_reflns_theta_min         4.514
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.328
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45079
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.44a (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    1.115
_exptl_crystal_description       prism
_exptl_crystal_F_000             616
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.233
_refine_diff_density_min         -0.383
_refine_diff_density_rms         0.104
_refine_ls_abs_structure_details
;
 Flack x determined using 1342 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.002(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     185
_refine_ls_number_reflns         3246
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0352
_refine_ls_R_factor_gt           0.0349
_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^)+(0.0687P)^2^+0.0883P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0916
_refine_ls_wR_factor_ref         0.0919
_reflns_Friedel_coverage         0.723
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.983
_reflns_number_gt                3208
_reflns_number_total             3246
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00333_si_002.cif
_cod_data_source_block           eo015
_cod_original_cell_volume        1698.186(17)
_cod_database_code               4034267
_shelx_shelxl_version_number     2016/4
_shelx_estimated_absorpt_t_max   0.836
_shelx_estimated_absorpt_t_min   0.619
_reflns_odcompleteness_completeness 99.94
_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, All N(H) groups
 At 1.5 times of:
  All B(H,H,H) groups, All C(H,H,H) groups
2.a Riding coordinates:
 N1(H1)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13)
2.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), B1(H1C,H1D,H1E)
;
_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 1.473
_oxdiff_exptl_absorpt_empirical_full_min 0.550