Construction of Chiral Tricyclic Indoles through a Rhodium-Catalyzed Asymmetric Arylation Protocol.
Wu, Chun-Yan; Yu, Yue-Na; Xu, Ming-Hua; Organic letters 19 (2017) 384–387; doi:10.1021/acs.orglett.6b03585

data_1555996
_publ_section_title
;
 Construction of Chiral Tricyclic Indoles through a Rhodium-Catalyzed
 Asymmetric Arylation Protocol.
;
_journal_issue                   2
_journal_name_full               'Organic letters'
_journal_page_first              384
_journal_page_last               387
_journal_paper_doi               10.1021/acs.orglett.6b03585
_journal_volume                  19
_journal_year                    2017
_chemical_absolute_configuration rm
_chemical_formula_moiety         '1(C21 H22 Br N O2)'
_chemical_formula_sum            'C21 H22 Br N O2'
_chemical_formula_weight         400.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-12-26
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2016.12.12 svn.r3370 for OlexSys, GUI svn.r5282)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.885(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.0625(2)
_cell_length_b                   19.5089(7)
_cell_length_c                   16.3468(6)
_cell_measurement_reflns_used    4483
_cell_measurement_temperature    100
_cell_measurement_theta_max      24.00
_cell_measurement_theta_min      2.44
_cell_volume                     1919.44(12)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0424
_diffrn_reflns_av_unetI/netI     0.0848
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            9417
_diffrn_reflns_point_group_measured_fraction_full 0.930
_diffrn_reflns_point_group_measured_fraction_max 0.930
_diffrn_reflns_theta_full        25.008
_diffrn_reflns_theta_max         25.008
_diffrn_reflns_theta_min         1.255
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.155
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5260
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.0973 before and 0.0614 after correction. The Ratio of minimum to maximum transmission is 0.7055. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.385
_exptl_crystal_description       block
_exptl_crystal_F_000             824
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         3.172
_refine_diff_density_min         -0.970
_refine_diff_density_rms         0.166
_refine_ls_abs_structure_details
;
 Flack x determined using 1725 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.071(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.901
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     494
_refine_ls_number_reflns         6296
_refine_ls_number_restraints     656
_refine_ls_restrained_S_all      0.900
_refine_ls_R_factor_all          0.1211
_refine_ls_R_factor_gt           0.1029
_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^)+(0.3000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2877
_refine_ls_wR_factor_ref         0.3146
_reflns_Friedel_coverage         0.820
_reflns_Friedel_fraction_full    0.866
_reflns_Friedel_fraction_max     0.866
_reflns_number_gt                4920
_reflns_number_total             6296
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b03585_si_002.cif
_cod_data_source_block           p
_cod_database_code               1555996
_shelx_shelxl_version_number     2014/7
_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
 C28-C22 = C27-C26 = C28-C27 = C24-C22 = C25-C24 = C26-C25
 1.39 with sigma of 0.02
 C7-C4 \\sim C7-C4A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Br1 \\sim O1 \\sim C10 \\sim N1 \\sim O2 \\sim C13 \\sim C15 \\sim C11 \\sim
C14 \\sim C9 \\sim C8 \\sim C7 \\sim C12 \\sim C19 \\sim C18 \\sim C17 \\sim
C16 \\sim C21 \\sim C20: within 2A with sigma of 0.008 and sigma for terminal
atoms of 1.7
Uanis(C3A) \\sim Ueq, Uanis(C4A) \\sim Ueq, Uanis(C5A) \\sim Ueq, Uanis(C6A)
\\sim Ueq, : with sigma of 0.005 and sigma for terminal atoms of 0.01
: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C1) \\sim
Ueq, Uanis(C4) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of
0.01
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: Br1A(0.5) H7A(0.6) H7B(0.4) C3(0.6) H3(0.6) C2(0.6) H2(0.6)
 C1(0.6) C6(0.6) H6(0.6) C5(0.6) H5(0.6) C4(0.6) H24A(0.5) H24(0.5) C23(0.5)
 C30(0.5) H30(0.5) C27(0.5) H27(0.5) C28(0.5) H28(0.5) C29(0.5) H29(0.5)
 Br0A(0.5) C22(0.5) C1A(0.4) C2A(0.4) H2A(0.4) C3A(0.4) H3A(0.4) C4A(0.4)
 C5A(0.4) H5A(0.4) C6A(0.4) H6A(0.4)
6.a Ternary CH refined with riding coordinates:
 C31(H31), C7(H7A), C7(H7B)
6.b Secondary CH2 refined with riding coordinates:
 C32(H32A,H32B), C8(H8A,H8B)
6.c Aromatic/amide H refined with riding coordinates:
 C44(H44), C45(H45), C42(H42), C0AA(H0AA), N2(H2B), C39(H39), N1(H1), C15(H15),
  C25(H25), C3(H3), C2(H2), C6(H6), C5(H5), C24(H24A), C24(H24), C30(H30),
 C27(H27), C28(H28), C29(H29), C19(H19), C18(H18), C21(H21), C20(H20), C2A(H2A),
  C3A(H3A), C5A(H5A), C6A(H6A)
6.d Fitted hexagon refined as free rotating group:
 C44(C45,C40,C41,C42,C0AA), C3(C2,C1,C6,C5,C4), C19(C18,C17,C16,C21,C20),
 C1A(C2A,C3A,C4A,C5A,C6A)
6.e Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C13(H13A,H13B,H13C), C11(H11A,H11B,H11C), C36(H36A,H36B,
 H36C), C12(H12A,H12B,H12C), C37(H37A,H37B,H37C)
;
_olex2_submission_special_instructions 'No special instructions were received'