Pd-catalyzed enantio-and diastereoselective synthesis of N-N atropisomeric indoles via N-alkylation reaction
Lu, Xiao; Xu, Yongqiang; Li, Wenkai; Zhou, Yuhan; Qu, Jingping; Wang, Baomin; Chemical Communications  (2026) –; doi:10.1039/D6CC00641H

data_7135640
_publ_section_title
;
 Pd-catalyzed enantio- and diastereoselective synthesis of N-N
 atropisomeric indoles <i>via N</i>-alkylation reaction.
;
_journal_issue                   28
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              7385
_journal_page_last               7388
_journal_paper_doi               10.1039/d6cc00641h
_journal_volume                  62
_journal_year                    2026
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C36 H40 N2 O5 S'
_chemical_formula_sum            'C36 H40 N2 O5 S'
_chemical_formula_weight         612.76
_chemical_name_systematic
'(1S,2R,4S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl 1-((N-((Sa , S)-1-(benzyloxy)allyl)-4-methylphenyl)sulfonamido)-1H-indole-2-carboxylate'
_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             2025-06-16
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-11-30 deposited with the CCDC.	2026-03-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.589(3)
_cell_length_b                   14.436(4)
_cell_length_c                   21.145(7)
_cell_measurement_reflns_used    9931
_cell_measurement_temperature    120.00
_cell_measurement_theta_max      26.09
_cell_measurement_theta_min      2.39
_cell_volume                     3232.3(17)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      120.00
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1054
_diffrn_reflns_av_unetI/netI     0.0515
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            64551
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.662
_diffrn_reflns_theta_min         2.151
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.145
_exptl_absorpt_correction_T_max  0.6731
_exptl_absorpt_correction_T_min  0.5914
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1666 before and 0.1356 after correction.
The Ratio of minimum to maximum transmission is 0.8786.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.259
_exptl_crystal_description       block
_exptl_crystal_F_000             1304
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: DCM'
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.190
_refine_diff_density_min         -0.350
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 2377 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     409
_refine_ls_number_reflns         6788
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0524
_refine_ls_R_factor_gt           0.0415
_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^)+(0.0455P)^2^+0.7479P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0946
_refine_ls_wR_factor_ref         0.1015
_reflns_Friedel_coverage         0.783
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                5931
_reflns_number_total             6788
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc00641h2.cif
_cod_data_source_block           1
_cod_depositor_comments          'Adding full bibliography for 7135640.cif.'
_cod_original_cell_volume        3232.5(17)
_cod_database_code               7135640
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.972
_shelx_estimated_absorpt_t_min   0.931
_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:
 C00A(H00A), C00L(H00L), C00T(H00T)
2.b Secondary CH2 refined with riding coordinates:
 C00J(H00B,H00D), C00N(H00E,H00F), C00Q(H00H,H00I), C00Y(H00R,H00S)
2.c Aromatic/amide H refined with riding coordinates:
 C00C(H00C), C00G(H00G), C00K(H00K), C00M(H00M), C00O(H00O), C00P(H00P),
 C00U(H00U), C00V(H00V), C00X(H00X), C011(H011), C012(H012), C013(H013),
 C014(H014), C015(H015), C018(H018)
2.d Idealised Me refined as rotating group:
 C00W(H00J,H00N,H00Q), C00Z(H00W,H00Y,H), C010(H01A,H01B,H01C), C017(H01F,H01G,
 H01H)
;
_shelx_res_checksum              84600
_shelx_hkl_checksum              92568
_olex2_submission_special_instructions 'No special instructions were received'