Enantioselective α-Aminophosphonate Functionalization of Indole Ring through an Organocatalyzed Friedel-Crafts Reaction.
Maestro, Aitor; Martinez de Marigorta, Edorta; Palacios, Francisco; Vicario, Javier; The Journal of organic chemistry 84 (2019) 1094–1102; doi:10.1021/acs.joc.8b02843

data_4035962
_publ_section_title
;
 Enantioselective \a-Aminophosphonate Functionalization of Indole Ring
 through an Organocatalyzed Friedel-Crafts Reaction.
;
_journal_issue                   2
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              1094
_journal_page_last               1102
_journal_paper_doi               10.1021/acs.joc.8b02843
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C24 H39 N2 O6 P S'
_chemical_formula_sum            'C24 H39 N2 O6 P S'
_chemical_formula_weight         514.6
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      4
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-06T15:43:16-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 104.555(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.75922(14)
_cell_length_b                   24.0052(5)
_cell_length_c                   10.1828(2)
_cell_measurement_reflns_used    7306
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      74.353
_cell_measurement_theta_min      4.443
_cell_volume                     1362.60(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (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      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2012
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1
_diffrn_measured_fraction_theta_max 1
_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   -115.00 -20.00   1.00    1.00    --  -42.13 -77.00-150.00   95
  2  \w    -33.00  30.00   1.00    1.00    --  -42.13  57.00 -30.00   63
  3  \w    -63.00  25.00   1.00    1.00    --  -42.13  38.00 120.00   88
  4  \w    -57.00 -17.00   1.00    1.00    --  -42.13 -57.00-120.00   40
  5  \w    -68.00  -9.00   1.00    1.00    --  -42.13 125.00-180.00   59
  6  \w     44.00  69.00   1.00    2.00    --  107.93 -45.00  30.00   25
  7  \w     79.00 106.00   1.00    2.00    --  107.93  61.00 150.00   27
  8  \w     37.00 118.00   1.00    2.00    --  107.93-125.00  60.00   81
  9  \w     79.00 109.00   1.00    2.00    --  107.93  61.00-120.00   30
 10  \w     58.00 116.00   1.00    2.00    --  107.93-125.00-150.00   58
 11  \w     75.00 102.00   1.00    2.00    --  107.93  77.00 150.00   27
 12  \w     34.00  69.00   1.00    2.00    --  107.93 -30.00 -90.00   35
 13  \w     36.00  76.00   1.00    2.00    --  107.93 -45.00   0.00   40
 14  \w     81.00 106.00   1.00    2.00    --  107.93  61.00-180.00   25
 15  \w     34.00  68.00   1.00    2.00    --  107.93 -30.00  90.00   34
 16  \w     33.00  58.00   1.00    2.00    --  107.93 -30.00-180.00   25
 17  \w     79.00 106.00   1.00    2.00    --  107.93  61.00-150.00   27
 18  \w     39.00  67.00   1.00    2.00    --  107.93 -45.00-150.00   28
 19  \w     83.00 119.00   1.00    2.00    --  107.93  45.00-180.00   36
 20  \w     39.00  69.00   1.00    2.00    --  107.93 -30.00 120.00   30
 21  \w     75.00 101.00   1.00    2.00    --  107.93  77.00-150.00   26
 22  \w    121.00 149.00   1.00    2.00    --  107.93  77.00-150.00   28
 23  \w     79.00 106.00   1.00    2.00    --  107.93  61.00 -90.00   27
 24  \w     75.00 101.00   1.00    2.00    --  107.93  77.00-180.00   26
 25  \w     34.00  66.00   1.00    2.00    --  107.93 -30.00-120.00   32
 26  \w     76.00 101.00   1.00    2.00    --  107.93  77.00-120.00   25
 27  \w     76.00 101.00   1.00    2.00    --  107.93  77.00 120.00   25
 28  \w     33.00  68.00   1.00    2.00    --  107.93 -30.00 -60.00   35
 29  \w     83.00 109.00   1.00    2.00    --  107.93  45.00-120.00   26
 30  \w     82.00 126.00   1.00    2.00    --  107.93  45.00 -90.00   44
 31  \w     44.00  69.00   1.00    2.00    --  107.93 -30.00-150.00   25
 32  \w    113.00 140.00   1.00    2.00    --  107.93  61.00-180.00   27
 33  \w     82.00 145.00   1.00    2.00    --  107.93  45.00-150.00   63
 34  \w     86.00 128.00   1.00    2.00    --  107.93  45.00 150.00   42
 35  \w     78.00 139.00   1.00    2.00    --  107.93  71.00 -95.96   61
 36  \w     51.00  78.00   1.00    1.00    --   42.13-125.00 150.00   27
 37  \w     14.00  41.00   1.00    1.00    --   42.13-125.00 150.00   27
 38  \w     50.00  84.00   1.00    1.00    --   42.13-125.00   0.00   34
 39  \w     47.00 110.00   1.00    2.00    --  107.93 -94.00-150.00   63
 40  \w     56.00  99.00   1.00    2.00    --  107.93 -94.00  90.00   43
 41  \w    109.00 143.00   1.00    2.00    --  107.93  30.00 -30.00   34
 42  \w     41.00  69.00   1.00    2.00    --  107.93 -45.00  60.00   28
 43  \w     54.00 109.00   1.00    2.00    --  107.93 -77.00 -90.00   55
 44  \w   -115.00 -30.00   1.00    1.00    --  -42.13 -57.00 -30.00   85
 45  \w   -118.00 -10.00   1.00    1.00    --  -42.13 -77.00  60.00  108
;
_diffrn_measurement_device       'four-circle\k-geometry diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0061755
_diffrn_orient_matrix_UB_12      -0.0204035
_diffrn_orient_matrix_UB_13      -0.1442871
_diffrn_orient_matrix_UB_21      -0.2687623
_diffrn_orient_matrix_UB_22      -0.0136746
_diffrn_orient_matrix_UB_23      -0.0239268
_diffrn_orient_matrix_UB_31      -0.064098
_diffrn_orient_matrix_UB_32      0.05928
_diffrn_orient_matrix_UB_33      -0.0552057
_diffrn_radiation_monochromator  'Multilayer optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0471
_diffrn_reflns_av_unetI/netI     0.0721
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 1
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            14836
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.465
_diffrn_reflns_theta_max         67.465
_diffrn_reflns_theta_min         3.683
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.938
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.77355
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
        Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.254
_exptl_crystal_description       needle
_exptl_crystal_F_000             552
_exptl_crystal_size_max          0.865
_exptl_crystal_size_mid          0.135
_exptl_crystal_size_min          0.077
_refine_diff_density_max         0.253
_refine_diff_density_min         -0.317
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
The Friedel pair coverage of the experiment is almost complete (94%).
Analysis of the absolute structure using likelihood methods
(Hooft, Straver & Spek, 2008) was performed using OLEX2 (Dolomanov, 2009).
 The results indicated that the absolute structure had been correctly
 assigned. The method calculated that the probability that the structure 
is inverted is smaller than 10-99. The absolute structure parameter y 
(Hooft, Straver & Spek, 2008) was calculated using PLATON (Spek,
2010). The resulting value was y=-0.003(12), which together with Flack
parameter value, indicate that the absolute structure has sureley been
determined correctly.

Flack, H. D. (1983), Acta Cryst. A39, 876-881
Flack & G. Bernardinelli, Acta Cryst. 1999, A55, 908-915; 
H. D. Flack & G. Bernardinelli, J. Appl. Cryst. 2000, 33, 1143-1148.

R. W. W. Hooft, L. H. Straver & A. L. Spek, J. Appl. Cryst. 2008, 41, 96-103
Dolomanov, O.V. (2009) OLEX2, J. Appl. Cryst., 42, 339-341. 
Spek, A.L. (2003). J. Appl. Cryst. 36, 7-13.
Spek, A.L. (2009). Acta Cryst. D65, 148-155.
A. L. Spek (2010) PLATON, Utrecht, The Netherlands; 
A. L. Spek, J. Appl. Cryst. 2003, 36, 7-13
A. L. Thompson & D. J. Watkin, Tetrahedron: Asymmetry 2009, 20, 712--717
;
_refine_ls_abs_structure_Flack   0.006(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     360
_refine_ls_number_reflns         4771
_refine_ls_number_restraints     75
_refine_ls_restrained_S_all      1.105
_refine_ls_R_factor_all          0.0413
_refine_ls_R_factor_gt           0.038
_refine_ls_shift/su_max          0
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0407P)^2^+0.3006P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0902
_refine_ls_wR_factor_ref         0.0931
_reflns_Friedel_coverage         0.896
_reflns_Friedel_fraction_full    0.943
_reflns_Friedel_fraction_max     0.943
_reflns_number_gt                4490
_reflns_number_total             4771
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02843_si_003.cif
_cod_data_source_block           a20180314_am708rem
_cod_database_code               4035962