Catalytic enantioselective hydrophosphinylation of <i>in situ</i>-generated indole-derived vinylogous imines to access 3-(1-diphenylphosphoryl-arylmethyl)indoles.
Jia, Yun-Qing; Zhao, Jian-Qiang; Wang, Zhen-Hua; You, Yong; Zhang, Yan-Ping; Jin, Xin; Zhou, Ming-Qiang; Ge, Zhen-Zhen; Yuan, Wei-Cheng; Chemical communications (Cambridge, England) 58 (2022) 12062–12065; doi:10.1039/d2cc04763b

data_7130833
_publ_section_title
;
 Catalytic enantioselective hydrophosphinylation of <i>in
 situ</i>-generated indole-derived vinylogous imines to access
 3-(1-diphenylphosphoryl-arylmethyl)indoles.
;
_journal_issue                   86
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              12062
_journal_page_last               12065
_journal_paper_doi               10.1039/d2cc04763b
_journal_volume                  58
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C29 H26 N O2 P, C2 H6 O'
_chemical_formula_sum            'C31 H32 N O3 P'
_chemical_formula_weight         497.54
_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     direct
_audit_block_doi                 10.5517/ccdc.csd.cc28kjcr
_audit_creation_date             2020-09-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-08-07 deposited with the CCDC.	2022-09-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.45953(19)
_cell_length_b                   13.5092(3)
_cell_length_c                   19.3396(4)
_cell_measurement_reflns_used    10033
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.9750
_cell_measurement_theta_min      3.9750
_cell_volume                     2732.68(10)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega  -14.00   11.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000  -90.0000 25

  2 omega  -61.00  -36.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000  -90.0000 25

  3 omega  -56.00   35.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   77.0000   90.0000 91

  4 omega  -50.00  -18.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -57.0000  -30.0000 32

  5 omega  -10.00   15.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  110.0000  -77.9103 25

  6 omega   18.00   46.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   57.0000    0.0000 28

  7 omega   21.00   67.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000  120.0000 46

  8 omega   26.00   52.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000   30.0000 26

  9 omega   63.00   96.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000   30.0000 33

 10 omega   23.00   56.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   19.0000   60.0000 33

 11 omega   30.00   79.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   37.0000   90.0000 49

 12 omega   14.00   84.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   37.0000   60.0000 70

 13 omega  -32.00   63.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -77.0000  150.0000 95

 14 omega   -6.00   22.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  104.0000   93.4890 28

 15 omega   -1.00   34.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   19.0000    0.0000 35

 16 omega  -16.00   72.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -89.0000 -102.0000 88

 17 omega   58.00   88.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000  -90.0000 30

 18 omega   24.00   50.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000 -120.0000 26

 19 omega   39.00   85.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000   90.0000 46

 20 omega   75.00  109.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   19.0000   60.0000 34

 21 omega   18.00   53.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   57.0000 -120.0000 35

 22 omega    8.00   33.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000   90.0000 25

 23 omega   75.00  100.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000    0.0000 25

 24 omega   19.00   45.00   1.0000    2.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000    0.0000 26

 25 omega  124.00  174.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -90.0000 50

 26 omega   88.00  114.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000    0.0000 26

 27 omega   82.00  110.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  -60.0000 28

 28 omega   79.00  112.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -90.0000 33

 29 omega   85.00  111.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  -30.0000 26

 30 omega   88.00  151.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -30.0000 63

 31 omega  101.00  153.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000  120.0000 52

 32 omega  110.00  175.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -120.0000 65

 33 omega  127.00  160.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000   60.0000 33

 34 omega   88.00  114.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000 -120.0000 26

 35 omega  102.00  162.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000   90.0000 60

 36 omega   79.00  105.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -120.0000 26

 37 omega   88.00  114.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -60.0000 26

 38 omega  145.00  171.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000   30.0000 26

 39 omega   86.00  129.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000   30.0000 43

 40 omega  103.00  166.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000   60.0000 63

 41 omega   89.00  118.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000 -120.0000 29

 42 omega   83.00  160.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000    0.0000 77

 43 omega  129.00  171.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000    0.0000 42

 44 omega   79.00  105.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -30.0000 26

 45 omega   39.00   92.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  120.0000 53

 46 omega   42.00   97.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -30.0000 55

 47 omega   79.00  104.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000    0.0000 25

 48 omega   92.00  118.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   30.0000 26

 49 omega   89.00  115.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000  -30.0000 26

 50 omega   88.00  114.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000    0.0000 26

 51 omega   64.00  103.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  -90.0000 39

 52 omega   79.00  105.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -60.0000 26

 53 omega   86.00  115.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  -90.0000 29

 54 omega   88.00  114.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -90.0000 26

 55 omega   67.00   93.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000    0.0000 26

 56 omega  135.00  161.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -60.0000 26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1003014000
_diffrn_orient_matrix_UB_12      -0.0405651000
_diffrn_orient_matrix_UB_13      -0.0509782000
_diffrn_orient_matrix_UB_21      0.1074809000
_diffrn_orient_matrix_UB_22      0.0295451000
_diffrn_orient_matrix_UB_23      0.0504214000
_diffrn_orient_matrix_UB_31      -0.0088173000
_diffrn_orient_matrix_UB_32      -0.1024142000
_diffrn_orient_matrix_UB_33      0.0347014000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0406
_diffrn_reflns_av_unetI/netI     0.0269
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            24771
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.069
_diffrn_reflns_theta_max         67.069
_diffrn_reflns_theta_min         3.992
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.138
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69126
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    1.209
_exptl_crystal_description       prism
_exptl_crystal_F_000             1056
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.218
_refine_diff_density_min         -0.200
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 1849 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.006(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     333
_refine_ls_number_reflns         4884
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0420
_refine_ls_R_factor_gt           0.0391
_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^)+(0.0710P)^2^+0.2312P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1048
_refine_ls_wR_factor_ref         0.1077
_reflns_Friedel_coverage         0.764
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                4553
_reflns_number_total             4884
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc04763b2.cif
_cod_data_source_block           202009174
_cod_depositor_comments          'Adding full bibliography for 7130833.cif.'
_cod_original_cell_volume        2732.69(10)
_cod_database_code               7130833
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C20H20N4O4P1
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.839
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 C31-C30
 1.75 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C13(H13)
3.b Secondary CH2 refined with riding coordinates:
 C30(H30A,H30B)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C15(H15), C16(H16), C18(H18), C19(H19), C21(H21), C22(H22), C23(H23),
  C24(H24)
3.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C29(H29A,H29B,H29C), C31(H31A,H31B,H31C)
3.e Idealised tetrahedral OH refined as rotating group:
 O3(H3A)
;
_shelx_res_checksum              60497
_shelx_hkl_checksum              91407
_olex2_submission_special_instructions 'No special instructions were received'