Asymmetric synthesis of functionalized 2,3-dihydrobenzofurans using salicyl <i>N</i>-phosphonyl imines facilitated by group-assisted purification (GAP) chemistry.
Rouh, Hossein; Tang, Yao; Zhang, Sai; Ali, Ahmed I. M.; Unruh, Daniel; Surowiec, Kazimierz; Li, Guigen; Organic & biomolecular chemistry 19 (2021) 10319–10325; doi:10.1039/d1ob02078a

data_7158402
_publ_section_title
;
 Asymmetric synthesis of functionalized 2,3-dihydrobenzofurans using
 salicyl <i>N</i>-phosphonyl imines facilitated by group-assisted
 purification (GAP) chemistry.
;
_journal_issue                   47
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              10319
_journal_page_last               10325
_journal_paper_doi               10.1039/d1ob02078a
_journal_volume                  19
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H40 N3 O6 P, 1(C1 H1 Cl3)'
_chemical_formula_sum            'C27 H41 Cl3 N3 O6 P'
_chemical_formula_weight         640.95
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-03-02
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.03.28 svn.rd84adfe8 for Rigaku Oxford Diffraction, GUI svn.r6032)
;
_audit_update_record
;
2021-10-08 deposited with the CCDC.	2021-11-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.88480(10)
_cell_length_b                   12.80570(10)
_cell_length_c                   21.2120(3)
_cell_measurement_reflns_used    23450
_cell_measurement_temperature    99.9(3)
_cell_measurement_theta_max      77.3240
_cell_measurement_theta_min      4.0030
_cell_volume                     3228.32(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(3)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -80.00  25.00   0.50    0.68    --  -47.95  98.00-149.00  210
  2  \w   -159.00 -73.00   0.50    2.72    --  -86.25 -40.00 -45.00  172
  3  \w    102.00 178.00   0.50    2.72    --  107.74  92.00 -47.00  152
  4  \w     35.00 105.00   0.50    2.72    --  107.74 -98.00 104.00  140
  5  \w   -120.00 -73.00   0.50    0.68    --  -47.95-125.00-120.00   94
  6  \w    -24.00  28.00   0.50    0.68    --  -47.95  19.00 150.00  104
  7  \w   -120.00 -73.00   0.50    0.68    --  -47.95-125.00 -90.00   94
  8  \w   -120.00 -73.00   0.50    0.68    --  -47.95-125.00 -60.00   94
  9  \w    -41.00 -13.00   0.50    2.72    --  -86.25  38.00-150.00   56
 10  \w    -41.00 -13.00   0.50    2.72    --  -86.25  38.00-180.00   56
 11  \w    -41.00 -13.00   0.50    2.72    --  -86.25  38.00-120.00   56
 12  \w    -43.00 -13.00   0.50    2.72    --  -86.25  40.00 108.00   60
 13  \w     35.00  68.00   0.50    2.72    --  107.74 -57.00-180.00   66
 14  \w     35.00 106.00   0.50    2.72    --  107.74 -99.00-180.00  142
 15  \w     35.00  68.00   0.50    2.72    --  107.74 -57.00 -90.00   66
 16  \w     35.00  68.00   0.50    2.72    --  107.74 -57.00 -30.00   66
 17  \w     35.00  68.00   0.50    2.72    --  107.74 -57.00  60.00   66
 18  \w     35.00 106.00   0.50    2.72    --  107.74 -99.00  60.00  142
 19  \w     95.00 178.00   0.50    2.72    --  107.74  19.00  30.00  166
 20  \w     35.00  68.00   0.50    2.72    --  107.74 -57.00-150.00   66
 21  \w     35.00 106.00   0.50    2.72    --  107.74 -99.00 120.00  142
 22  \w     95.00 178.00   0.50    2.72    --  107.74 125.00 150.00  166
 23  \w     35.00  68.00   0.50    2.72    --  107.74 -57.00-120.00   66
 24  \w   -120.00 -53.00   0.50    0.68    --  -47.95 -77.00 -60.00  134
 25  \w   -120.00 -25.00   0.50    0.68    --  -47.95 -77.00  30.00  190
 26  \w   -120.00 -25.00   0.50    0.68    --  -47.95 -77.00 120.00  190
 27  \w     33.00 119.00   0.50    0.68    --   47.95  57.00-120.00  172
 28  \w     25.00 120.00   0.50    0.68    --   47.95  77.00 120.00  190
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0295615000
_diffrn_orient_matrix_UB_12      0.0522203000
_diffrn_orient_matrix_UB_13      -0.0633073000
_diffrn_orient_matrix_UB_21      0.1157730000
_diffrn_orient_matrix_UB_22      0.0316854000
_diffrn_orient_matrix_UB_23      0.0264756000
_diffrn_orient_matrix_UB_31      0.0503026000
_diffrn_orient_matrix_UB_32      -0.1035876000
_diffrn_orient_matrix_UB_33      -0.0238419000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0463
_diffrn_reflns_av_unetI/netI     0.0314
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            29971
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.070
_diffrn_reflns_theta_max         67.070
_diffrn_reflns_theta_min         4.032
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.395
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.672
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.99a (Rigaku Oxford Diffraction, 2021)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.319
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1352
_exptl_crystal_recrystallization_method
'Vacuum filtration of the molecule from chloroform'
_exptl_crystal_size_max          0.145
_exptl_crystal_size_mid          0.112
_exptl_crystal_size_min          0.058
_refine_diff_density_max         0.271
_refine_diff_density_min         -0.264
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 2172 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.004(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     443
_refine_ls_number_reflns         5732
_refine_ls_number_restraints     271
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0361
_refine_ls_R_factor_gt           0.0323
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0432P)^2^+0.7253P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0800
_refine_ls_wR_factor_ref         0.0828
_reflns_Friedel_coverage         0.770
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                5323
_reflns_number_total             5732
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob02078a2.cif
_cod_data_source_block           2
_cod_depositor_comments          'Adding full bibliography for 7158402.cif.'
_cod_database_code               7158402
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C68  H104  N24  O44  P4  Cl1  '
_shelx_estimated_absorpt_t_max   0.827
_shelx_estimated_absorpt_t_min   0.639
_reflns_odcompleteness_completeness 99.91
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C27-Cl1 = C27-Cl2 = C27-Cl3 = C28-Cl4 = C28-Cl5 = C28-Cl6 = C29-Cl7 = C29-Cl8
 = C29-Cl9
 1.7367 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl1 \\sim Cl2 \\sim Cl3 \\sim C27 \\sim Cl4 \\sim Cl5 \\sim Cl6 \\sim C28 \\sim
C29 \\sim Cl7 \\sim Cl8 \\sim Cl9: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
4. Rigid body (RIGU) restrains
 Cl1, Cl2, Cl3, C27, Cl4, Cl5, Cl6, C28, C29, Cl7, Cl8, Cl9
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 1*[Sof(Cl1)+Sof(Cl2)+Sof(Cl3)+Sof(C27)+Sof(H27)]+1*[Sof(Cl4)+Sof(Cl5)+
 Sof(Cl6)+Sof(C28)+Sof(H28)]+1*[Sof(Cl7)+Sof(Cl8)+Sof(Cl9)+Sof(C29)+Sof(H29)]=1
 with esd of 0
 Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=Sof(C27)=Sof(H27)=FVAR(2)
 Sof(Cl4)=Sof(Cl5)=Sof(Cl6)=Sof(C28)=Sof(H28)=FVAR(3)
 Sof(Cl7)=Sof(Cl8)=Sof(Cl9)=Sof(C29)=Sof(H29)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C7(H7), C10(H10), C13(H13), C27(H27), C28(H28), C29(H29)
6.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C22(H22A,H22B), C25(H25A,
 H25B)
6.c Aromatic/amide H refined with riding coordinates:
 N3(H3), C16(H16), C17(H17), C18(H18), C19(H19)
6.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 C23(H23A,H23B,H23C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              38714
_olex2_date_sample_data_collection 2021-03-01
_olex2_date_sample_submission    2021-03-01
_olex2_exptl_crystal_mounting_method 'MiTeGen 50 micron MicroLoop'
_olex2_submission_original_sample_id Li21_05
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_diffrn_reflns_filtered   3404
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.253
_oxdiff_exptl_absorpt_empirical_full_min 0.742