Brønsted acid catalyzed asymmetric diels-alder reactions: stereoselective construction of spiro[tetrahydrocarbazole-3,3'-oxindole] framework.
Wang, Yang; Tu, Man-Su; Yin, Lei; Sun, Meng; Shi, Feng; The Journal of organic chemistry 80 (2015) 3223–3232; doi:10.1021/acs.joc.5b00198

data_4036137
_publ_section_title
;
 Br\/onsted acid catalyzed asymmetric diels-alder reactions:
 stereoselective construction of spiro[tetrahydrocarbazole-3,3'-oxindole]
 framework.
;
_journal_issue                   6
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              3223
_journal_page_last               3232
_journal_paper_doi               10.1021/acs.joc.5b00198
_journal_volume                  80
_journal_year                    2015
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C29 H25 Br N2 O3, C H2 Cl2'
_chemical_formula_sum            'C30 H27 Br Cl2 N2 O3'
_chemical_formula_weight         614.34
_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
_audit_creation_date             2014-12-26
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.856(4)
_cell_length_b                   15.543(7)
_cell_length_c                   17.398(7)
_cell_measurement_reflns_used    3659
_cell_measurement_temperature    130
_cell_measurement_theta_max      22.09
_cell_measurement_theta_min      2.62
_cell_volume                     2665.2(19)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_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  0.0678
_diffrn_reflns_av_unetI/netI     0.0750
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            19186
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         25.996
_diffrn_reflns_theta_min         1.757
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.779
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.5940
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0976 before and 0.0854 after correction.
The Ratio of minimum to maximum transmission is 0.7961.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.531
_exptl_crystal_description       block
_exptl_crystal_F_000             1256
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.764
_refine_diff_density_min         -0.831
_refine_diff_density_rms         0.177
_refine_ls_abs_structure_details
;
 Flack x determined using 1767 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.044(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     234
_refine_ls_number_reflns         5195
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0910
_refine_ls_R_factor_gt           0.0798
_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^)+(0.0962P)^2^+24.8211P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2091
_refine_ls_wR_factor_ref         0.2175
_reflns_Friedel_coverage         0.767
_reflns_Friedel_fraction_full    0.989
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                4560
_reflns_number_total             5195
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5b00198_si_002.cif
_cod_data_source_block           mo_dm14771_0m
_cod_original_cell_volume        2665(2)
_cod_database_code               4036137
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.776
_shelx_estimated_absorpt_t_min   0.665
_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. Others
 Fixed U11: Br1(0.01281)
 Fixed U12: Br1(-0.00036)
 Fixed U13: Br1(-0.00078)
 Fixed U22: Br1(0.03355)
 Fixed U23: Br1(0.00182)
 Fixed U33: Br1(0.02802)
 Fixed X: Br1(-0.12569) O1(0.32742) O2(0.58327) O3(0.486219) N1(0.72239)
 N2(0.166409) C1(0.71284) C2(0.782589) C3(0.75429) C4(0.64678) C5(0.572729)
 C6(0.60433) C7(0.55763) C8(0.63121) C9(0.604361) C10(0.51791) C11(0.39701)
 C12(0.45157) C13(0.50989) C14(0.55982) C15(0.537149) C16(0.298201)
 C17(0.302361) C18(0.328161) C19(0.22242) C20(0.091371) C21(0.06151)
 C22(0.16644) C23(0.04928) C24(0.485449) C25(0.367861) C26(0.34317)
 C27(0.444489) C28(0.57519) C29(0.59103)
 Fixed Y: Br1(-0.05006) O1(0.176909) O2(-0.108) O3(-0.07087) N1(0.1874)
 N2(0.07123) C1(0.18399) C2(0.237289) C3(0.22585) C4(0.16915) C5(0.1162)
 C6(0.12979) C7(0.09493) C8(0.128461) C9(0.112) C10(0.03375) C11(0.02427)
 C12(0.02599) C13(-0.059511) C14(-0.136999) C15(-0.131239) C16(0.102489) C17(-
 0.05181) C18(-0.13555) C19(-0.19286) C20(-0.16314) C21(-0.07924) C22(-
 0.019431) C23(0.12779) C24(0.021861) C25(0.04303) C26(0.037479) C27(0.01286)
 C28(-0.008019) C29(-0.004371)
 Fixed Z: Br1(-0.020361) O1(-0.014501) O2(-0.08901) O3(-0.203131) N1(-0.08415)
 N2(-0.019441) C1(-0.165791) C2(-0.2157) C3(-0.29528) C4(-0.31905) C5(-
 0.260091) C6(-0.18289) C7(-0.11225) C8(-0.05282) C9(0.03026) C10(0.04048) C11(-
 0.01863) C12(-0.10215) C13(-0.129431) C14(-0.24223) C15(-0.32427) C16(-
 0.01261) C17(-0.0007) C18(0.00719) C19(0.01533) C20(0.00435) C21(-0.007371)
 C22(-0.00831) C23(-0.023412) C24(0.121351) C25(0.15563) C26(0.23813)
 C27(0.279669) C28(0.25239) C29(0.17331)
3.a Ternary CH refined with riding coordinates:
 C10(H10), C12(H12)
3.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C14(H14A,H14B), C30(H30A,H30B)
3.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C18(H18), C19(H19), C20(H20),
 C25(H25), C26(H26), C27(H27), C28(H28), C29(H29)
3.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              270
_shelx_hkl_checksum              63505
_olex2_submission_special_instructions 'No special instructions were received'