Borane-catalyzed cascade Friedel–Crafts alkylation/[1,5]-hydride transfer/Mannich cyclization to afford tetrahydroquinolines
Zhang, Bei-Bei; Peng, Shuo; Wang, Feiyi; Lu, Cuifen; Nie, Junqi; Chen, Zuxing; Yang, Guichun; Ma, Chao; Chemical Science 13 (2022) 775–780; doi:10.1039/D1SC05629H

data_1565907
_publ_section_title
;
 Borane-catalyzed cascade Friedel--Crafts alkylation/[1,5]-hydride
 transfer/Mannich cyclization to afford tetrahydroquinolines
;
_journal_issue                   3
_journal_name_full               'Chemical Science'
_journal_page_first              775
_journal_page_last               780
_journal_paper_doi               10.1039/D1SC05629H
_journal_volume                  13
_journal_year                    2022
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C27 H27 N O3'
_chemical_formula_sum            'C27 H27 N O3'
_chemical_formula_weight         413.49
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-09-21
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-10-06 deposited with the CCDC.	2021-12-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.8450(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   5.76260(10)
_cell_length_b                   21.7654(3)
_cell_length_c                   36.0320(5)
_cell_measurement_reflns_used    21706
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      74.1720
_cell_measurement_theta_min      2.4370
_cell_volume                     4516.98(12)
_computing_cell_refinement       'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.979
_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     21.00  71.00   0.50    1.00    --   43.18  37.00  60.00  100
  2  \w     82.00 110.00   0.50    1.00    --   43.18  37.00  60.00   56
  3  \w     88.00 137.00   0.50    6.00    --  109.88 131.00 -55.00   98
  4  \w     82.00 175.00   0.50    6.00    --  109.88  77.00 -60.00  186
  5  \w     84.00 165.00   0.50    6.00    --  109.88 138.00 119.00  162
  6  \w     83.00 131.00   0.50    6.00    --  109.88  77.00 153.14   96
  7  \w     93.00 177.00   0.50    6.00    --  109.88  61.00 120.00  168
  8  \w     94.00 131.00   0.50    6.00    --  109.88 -45.00   0.00   74
  9  \w     80.00 120.00   0.50    6.00    --  109.88-131.00-126.00   80
 10  \w     95.00 121.00   0.50    6.00    --  109.88 -61.00-180.00   52
 11  \w     86.00 121.00   0.50    1.00    --   43.18  37.00-150.00   70
 12  \w     77.00 103.00   0.50    1.00    --   43.18  57.00-150.00   52
 13  \w     88.00 177.00   0.50    6.00    --  109.88  61.00 -90.00  178
 14  \w     85.00 170.00   0.50    6.00    --  109.88  77.00  30.00  170
 15  \w     89.00 178.00   0.50    6.00    --  109.88  61.00  60.00  178
 16  \w     84.00 170.00   0.50    6.00    --  109.88  77.00  90.00  172
 17  \w     81.00 156.00   0.50    6.00    --  109.88  77.00   0.00  150
 18  \w     89.00 177.00   0.50    6.00    --  109.88  61.00-150.00  176
 19  \w     47.00 101.00   0.50    6.00    --  109.88 -94.00  60.00  108
 20  \w     59.00  84.00   0.50    6.00    --  109.88-138.00  58.00   50
 21  \w     49.00 107.00   0.50    6.00    --  109.88 -94.00  90.00  116
 22  \w     39.00 103.00   0.50    1.00    --   43.18-138.00  58.00  128
 23  \w     45.00 137.00   0.50    6.00    --  109.88 -77.00 150.00  184
 24  \w     58.00 108.00   0.50    6.00    --  109.88 -94.00 -60.00  100
 25  \w     35.00  96.00   0.50    1.00    --   43.18-131.00-126.00  122
 26  \w     40.00  80.00   0.50    6.00    --  109.88 -61.00-180.00   80
 27  \w     22.00  56.00   0.50    1.00    --   43.18  37.00-150.00   68
 28  \w     21.00  47.00   0.50    1.00    --   43.18  57.00-150.00   52
 29  \w     34.00  84.00   0.50    6.00    --  109.88 -45.00   0.00  100
 30  \w    -70.00 -15.00   0.50    1.00    --  -43.18 -77.00 -30.00  110
 31  \w    -85.00 -15.00   0.50    1.00    --  -43.18 -77.00-150.00  140
 32  \w    -92.00 -61.00   0.50    6.00    --  -90.25 -77.00 -30.00   62
 33  \w    -92.00 -59.00   0.50    6.00    --  -90.25 -83.00 -60.73   66
 34  \w    -86.00 -61.00   0.50    6.00    --  -90.25 -77.00   0.00   50
 35  \w    -87.00 -61.00   0.50    6.00    --  -90.25 -77.00  60.00   52
 36  \w    -88.00 -61.00   0.50    6.00    --  -90.25 -77.00  90.00   54
 37  \w    -92.00 -61.00   0.50    6.00    --  -90.25 -77.00 128.69   62
 38  \w    -84.00 -59.00   0.50    6.00    --  -90.25 -83.00  81.05   50
 39  \w    -88.00 -62.00   0.50    6.00    --  -90.25 -75.00  20.66   52
 40  \w    -85.00 -59.00   0.50    6.00    --  -90.25 -82.00  -7.18   52
 41  \w    -86.00 -59.00   0.50    6.00    --  -90.25 -82.00 -28.95   54
 42  \w   -100.00 -61.00   0.50    6.00    --  -90.25 -77.00 -90.00   78
 43  \w    -94.00 -59.00   0.50    6.00    --  -90.25 -82.00-158.97   70
 44  \w    -98.00 -61.00   0.50    6.00    --  -90.25 -77.00-150.00   74
 45  \w    -98.00 -64.00   0.50    6.00    --  -90.25 -71.00-113.51   68
 46  \w    -93.00 -61.00   0.50    6.00    --  -90.25 -77.00-120.00   64
 47  \w   -117.00 -91.00   0.50    1.00    --  -43.18-131.00-126.00   52
 48  \w   -113.00 -14.00   0.50    1.00    --  -43.18 -77.00 -90.00  198
 49  \w    -77.00 -14.00   0.50    1.00    --  -43.18 -77.00  30.00  126
 50  \w    -56.00 -15.00   0.50    1.00    --  -43.18 -77.00 120.00   82
 51  \w    -91.00 -59.00   0.50    6.00    --  -90.25 -82.00 145.93   64
 52  \w    -86.00 -61.00   0.50    6.00    --  -90.25 -77.00 150.00   50
 53  \w    -95.00 -60.00   0.50    6.00    --  -90.25 -79.00 162.38   70
 54  \w    -93.00 -61.00   0.50    6.00    --  -90.25 -77.00 120.00   64
 55  \w   -101.00 -62.00   0.50    6.00    --  -90.25 -76.00 108.83   78
 56  \w    -94.00 -59.00   0.50    6.00    --  -90.25 -81.00  44.55   70
 57  \w    -96.00 -62.00   0.50    6.00    --  -90.25 -74.00   4.03   68
 58  \w   -106.00 -59.00   0.50    6.00    --  -90.25 -82.00 -45.36   94
 59  \w   -114.00 -89.00   0.50    1.00    --  -43.18-138.00  58.00   50
 60  \w   -108.00 -82.00   0.50    1.00    --  -43.18 -77.00 -30.00   52
 61  \w   -117.00 -81.00   0.50    1.00    --  -43.18 -77.00  30.00   72
 62  \w    -99.00 -20.00   0.50    1.00    --  -43.18 -57.00  60.00  158
 63  \w   -109.00 -20.00   0.50    1.00    --  -43.18 -57.00 150.00  178
 64  \w   -137.00-112.00   0.50    6.00    --  -90.25-138.00  58.00   50
 65  \w   -141.00-112.00   0.50    6.00    --  -90.25 -77.00 120.00   58
 66  \w   -151.00-126.00   0.50    6.00    --  -90.25 -77.00 150.00   50
 67  \w   -152.00-126.00   0.50    6.00    --  -90.25 -76.00 108.83   52
 68  \w   -145.00-120.00   0.50    6.00    --  -90.25 -77.00  60.00   50
 69  \w   -131.00-106.00   0.50    6.00    --  -90.25 -81.00  44.55   50
 70  \w   -153.00-100.00   0.50    6.00    --  -90.25 -83.00 -60.73  106
 71  \w   -140.00-115.00   0.50    6.00    --  -90.25-131.00-126.00   50
 72  \w   -109.00 -61.00   0.50    6.00    --  -90.25 -77.00-180.00   96
 73  \w   -140.00-115.00   0.50    6.00    --  -90.25 -77.00 -90.00   50
 74  \w   -144.00-116.00   0.50    6.00    --  -90.25 -77.00-120.00   56
 75  \w   -144.00-119.00   0.50    6.00    --  -90.25 -82.00 -45.36   50
 76  \w   -150.00 -61.00   0.50    6.00    --  -90.25 -79.00-127.89  178
 77  \w   -161.00-111.00   0.50    6.00    --  -90.25 -74.00   4.03  100
 78  \w   -158.00-118.00   0.50    6.00    --  -90.25 -79.00 162.38   80
 79  \w    -70.00 -45.00   0.50    1.00    --  -43.18 138.00 119.00   50
 80  \w    -88.00 -62.00   0.50    6.00    --  -90.25 138.00 119.00   52
 81  \w    -95.00 -70.00   0.50    1.00    --  -43.18 131.00 -55.00   50
 82  \w    -92.00 -66.00   0.50    6.00    --  -90.25 131.00 -55.00   52
;
_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      -0.0239956000
_diffrn_orient_matrix_UB_12      -0.0704551000
_diffrn_orient_matrix_UB_13      0.0006446000
_diffrn_orient_matrix_UB_21      0.0164995000
_diffrn_orient_matrix_UB_22      0.0009586000
_diffrn_orient_matrix_UB_23      0.0427466000
_diffrn_orient_matrix_UB_31      -0.2660025000
_diffrn_orient_matrix_UB_32      0.0065634000
_diffrn_orient_matrix_UB_33      0.0011962000
_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  0.0630
_diffrn_reflns_av_unetI/netI     0.0370
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            52460
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.928
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.172
_diffrn_reflns_theta_min         2.454
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.625
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65467
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.34b (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.216
_exptl_crystal_description       block
_exptl_crystal_F_000             1760
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.159
_refine_diff_density_min         -0.162
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
;
 Flack x determined using 3278 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.11(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     565
_refine_ls_number_reflns         8780
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0497
_refine_ls_R_factor_gt           0.0460
_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^)+(0.0681P)^2^+0.9532P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1235
_refine_ls_wR_factor_ref         0.1271
_reflns_Friedel_coverage         0.894
_reflns_Friedel_fraction_full    0.933
_reflns_Friedel_fraction_max     0.877
_reflns_number_gt                7972
_reflns_number_total             8780
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc05629h2.cif
_cod_data_source_block           ganshaolin
_cod_depositor_comments
;
Adding full bibliography for 1565906--1565907.cif.

2022-05-15
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C54 H54 N2 O6'
_cod_original_formula_weight         826.99
_cod_original_formula_moiety         '2(C27 H27 N O3)'
_cod_original_formula_units_Z            4
_cod_database_code               1565907
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.969
_reflns_odcompleteness_completeness 99.98
_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
2.a Ternary CH refined with riding coordinates:
 C32(H32), C3(H3), C33(H33), C2(H2), C1(H1), C34(H34)
2.b Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C57(H57A,H57B)
2.c Aromatic/amide H refined with riding coordinates:
 C47(H47), C40(H40), C43(H43), C16(H16), C5(H5), C14(H14), C15(H15), C8(H8),
 C12(H12), C44(H44), C53(H53), C37(H37), C38(H38), C18(H18), C13(H13), C45(H45),
  C46(H46), C49(H49), C19(H19), C7(H7), C52(H52), C21(H21), C22(H22), C20(H20),
 C51(H51), C50(H50)
2.d Idealised Me refined as rotating group:
 C61(H61A,H61B,H61C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C62(H62A,H62B,
 H62C), C27(H27A,H27B,H27C), C58(H58A,H58B,H58C)
;
_shelx_res_checksum              52098
_shelx_hkl_checksum              59799
_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 1.903
_oxdiff_exptl_absorpt_empirical_full_min 0.625