Diastereoselective synthesis of functionalised carbazoles via a sequential Diels‒Alder/ene reaction strategy
Cowell, Joseph; Abualnaja, Matokah; Morton, Stephanie; Linder, Ruth; Buckingham, Faye; Waddell, Paul G.; Probert, Michael R.; Hall, Michael J.; RSC Adv. 5 (2015) 16125–; doi:10.1039/C5RA00499C

data_7219490
_publ_section_title
;
 Diastereoselective synthesis of functionalised carbazoles via a
 sequential Diels--Alder/ene reaction strategy
;
_journal_issue                   21
_journal_name_full               'RSC Adv.'
_journal_page_first              16125
_journal_paper_doi               10.1039/C5RA00499C
_journal_volume                  5
_journal_year                    2015
_chemical_formula_moiety         'C28 H25 N3 O5 S, C H Cl3'
_chemical_formula_sum            'C29 H26 Cl3 N3 O5 S'
_chemical_formula_weight         634.94
_chemical_name_systematic
(3aS*,5S*,10bS*)-5-(hydroxy(o-tolyl)amino)-10-tosyl-4,5,10,10b-tetrahydropyrrolo[3,4-a]carbazole-1,3(2H,3aH)-dione
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-12-17
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2014.12.09 svn.r3114 for OlexSys, GUI svn.r4963)
;
_audit_update_record
;
2014-12-18 deposited with the CCDC.
2015-01-16 downloaded from the CCDC.
;
_cell_angle_alpha                104.231(4)
_cell_angle_beta                 95.071(4)
_cell_angle_gamma                109.240(4)
_cell_formula_units_Z            2
_cell_length_a                   10.0614(5)
_cell_length_b                   10.2208(5)
_cell_length_c                   15.2649(7)
_cell_measurement_reflns_used    7995
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      66.8641
_cell_measurement_theta_min      3.0366
_cell_volume                     1411.79(13)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      150.0
_diffrn_detector_area_resol_mean 10.3968
_diffrn_measured_fraction_theta_full 0.971
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details
;
  1 omega   19.00  107.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       40.3405   38.0000   90.0000 88

  2 omega    7.00   85.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       40.3405 -125.0000 -150.0000 78

  3 omega  -33.00   67.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       40.3405  -38.0000  -90.0000 100

  4 omega -117.00  -91.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  125.0000 -180.0000 26

  5 omega   59.00  127.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -90.0000   20.0000 68

  6 omega   64.00  139.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   15.0000   60.0000 75

  7 omega   57.00   83.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -90.0000  175.0000 26

  8 omega   16.00   56.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -77.0000  -60.0000 40

  9 omega   28.00   56.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -90.0000   20.0000 28

 10 omega   25.00   72.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -45.0000 -180.0000 47

 11 omega   18.00   69.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -30.0000  -90.0000 51

 12 omega   20.00   76.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -45.0000    0.0000 56

 13 omega   22.00   61.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -61.0000 -120.0000 39

 14 omega   23.00   63.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -30.0000  120.0000 40

 15 omega   21.00   47.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -94.0000 -120.0000 26

 16 omega  118.00  146.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   30.0000  -90.0000 28

 17 omega   20.00   92.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -58.0000   87.0000 72

 18 omega   56.00   81.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -94.0000 -120.0000 25

 19 omega   28.00   53.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -30.0000   60.0000 25

 20 omega   60.00   89.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -77.0000  -60.0000 29

 21 omega   16.00   69.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -30.0000 -150.0000 53

 22 omega   50.00   75.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -45.0000  -30.0000 25

 23 omega   88.00  114.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -90.0000  175.0000 26

 24 omega   48.00   74.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   15.0000  150.0000 26

 25 omega   81.00  169.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   15.0000  150.0000 88

 26 omega   22.00   68.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -77.0000   90.0000 46

 27 omega   72.00   97.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -77.0000   90.0000 25

 28 omega   52.00  116.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -92.0000  -69.0000 64

 29 omega   42.00   67.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -77.0000  -30.0000 25

 30 omega  102.00  127.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -77.0000  -30.0000 25

 31 omega   28.00   53.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000 -125.0000 -120.0000 25

 32 omega   59.00   85.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -61.0000 -180.0000 26

 33 omega   97.00  124.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -92.0000   91.0000 27
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1053722000
_diffrn_orient_matrix_UB_12      -0.0253532000
_diffrn_orient_matrix_UB_13      0.0668680000
_diffrn_orient_matrix_UB_21      0.0620975000
_diffrn_orient_matrix_UB_22      -0.1064905000
_diffrn_orient_matrix_UB_23      0.0272736000
_diffrn_orient_matrix_UB_31      0.1107894000
_diffrn_orient_matrix_UB_32      0.1260378000
_diffrn_orient_matrix_UB_33      0.0775224000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0264
_diffrn_reflns_av_unetI/netI     0.0239
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            13047
_diffrn_reflns_point_group_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         66.970
_diffrn_reflns_theta_min         3.039
_diffrn_source                   'Enhance Ultra (Cu) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.017
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86739
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
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    1.494
_exptl_crystal_description       block
_exptl_crystal_F_000             656
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.934
_refine_diff_density_min         -0.686
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     397
_refine_ls_number_reflns         4955
_refine_ls_number_restraints     411
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0537
_refine_ls_R_factor_gt           0.0490
_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^)+(0.0628P)^2^+1.8642P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1265
_refine_ls_wR_factor_ref         0.1296
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4523
_reflns_number_total             4955
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5ra00499c2.cif
_cod_data_source_block           mjh120026
_cod_original_cell_volume        1411.79(12)
_cod_database_code               7219490
_shelxl_version_number           2014/6
_reflns_odcompleteness_completeness 99.46
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_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, All O(H) groups
2. Restrained distances
 Cl1S-C1S \\sim Cl1P-C1P \\sim Cl1T-C1T \\sim Cl3T-C1T \\sim Cl2T-C1T \\sim
Cl2S-C1S \\sim Cl2P-C1P ~
 Cl3S-C1S \\sim Cl3P-C1P
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C1P) = Uanis(C1S) = Uanis(C1T)
Uanis(Cl3P) = Uanis(Cl3S) = Uanis(Cl3T)
Uanis(Cl1T) = Uanis(Cl1P) = Uanis(Cl1S)
Uanis(Cl2T) = Uanis(Cl2S) = Uanis(Cl2P)
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: C1P(0.65) H1P(0.65) Cl3P(0.65) Cl2P(0.65) Cl1P(0.65) C1S(0.25)
 H1S(0.25) Cl3S(0.25) Cl1S(0.25) Cl2S(0.25) C1T(0.1) H1T(0.1) Cl2T(0.1)
 Cl1T(0.1) Cl3T(0.1)
6.a Ternary CH refined with riding coordinates:
 C8(H8), C10(H10), C13(H13), C1P(H1P), C1S(H1S), C1T(H1T)
6.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
6.c Aromatic/amide H refined with riding coordinates:
 N2(H2), C2(H2A), C0AA(H0AA), C4(H4), C5(H5), C16(H16), C17(H17), C18(H18),
 C19(H19), C23(H23), C24(H24), C26(H26), C27(H27)
6.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C28(H28A,H28B,H28C)
6.e Idealised tetrahedral OH refined as rotating group:
 O3(H3)
;
_shelx_res_checksum              90771
_olex2_submission_special_instructions 'No special instructions were received'