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_7219494
_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         'C26 H26 N2 O6 S'
_chemical_formula_sum            'C26 H26 N2 O6 S'
_chemical_formula_weight         494.55
_chemical_name_systematic
'ethyl 3-((3aS*,4R*,10aS*,10bS*)-1,3-dioxo-10-tosyl-1,2,3,3a,4,10,10a,10b-octahydropyrrolo[3,4-a]carbazol-4-yl)propanoate'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-12-18
_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                90
_cell_angle_beta                 106.2054(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.0840(2)
_cell_length_b                   8.84163(10)
_cell_length_c                   18.0999(2)
_cell_measurement_reflns_used    27003
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      66.6150
_cell_measurement_theta_min      2.4920
_cell_volume                     2471.69(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_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    'XT (Sheldrick, 2008)'
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector_area_resol_mean 10.3968
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega   -1.00   25.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       34.0000   81.0000  -95.5864 26

  2 omega  -97.00  -18.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.9655  125.0000 -120.0000 79

  3 omega   24.00  115.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.9655   38.0000    0.0000 91

  4 omega   17.00   62.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.9655   38.0000 -120.0000 45

  5 omega   69.00   95.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.9655   38.0000 -120.0000 26

  6 omega   -3.00   95.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.9655 -125.0000  120.0000 98

  7 omega   16.00  118.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.9655   38.0000   90.0000 102

  8 omega    8.00   48.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.9655   77.0000  120.0000 40

  9 omega   13.00   55.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       46.0000   78.0000 -163.1291 42

 10 omega   18.00   47.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       50.0000   77.0000   58.0560 29

 11 omega   21.00   48.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000   -2.2956 27

 12 omega   69.00   96.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   79.0000 -113.7120 27

 13 omega   20.00   66.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   79.0000 -113.7120 46

 14 omega   28.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   77.0000  107.6284 88

 15 omega   28.00   56.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   78.0000  -55.8555 28

 16 omega   33.00   58.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   79.0000 -145.9565 25

 17 omega   35.00   68.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   77.0000 -113.6783 33

 18 omega   33.00   58.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   78.0000   24.9463 25

 19 omega   32.00   59.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   77.0000   68.9710 27

 20 omega   32.00   58.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   79.0000  163.3776 26

 21 omega  105.00  131.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   79.0000   -0.4747 26

 22 omega   33.00   59.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   79.0000   -0.4747 26

 23 omega   36.00   86.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   79.0000  -99.6759 50

 24 omega   36.00   62.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   79.0000  -41.7725 26

 25 omega   36.00   69.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   79.0000  133.7798 33

 26 omega   61.00  109.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   72.0000   22.6431 48

 27 omega   60.00  145.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000  120.0000 85

 28 omega  118.00  154.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -15.0000    0.0000 36

 29 omega   60.00  120.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000  -60.0000 60

 30 omega  140.00  165.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000  -60.0000 25

 31 omega  117.00  170.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000  150.0000 53

 32 omega   60.00   98.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000  150.0000 38

 33 omega   74.00  146.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   61.0000    0.0000 72

 34 omega   89.00  126.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   61.0000  -30.0000 37

 35 omega   45.00   74.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -94.0000  -30.0000 29

 36 omega   60.00  130.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000   30.0000 70

 37 omega  118.00  171.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000  -30.0000 53

 38 omega   60.00   88.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000  -30.0000 28

 39 omega   17.00   61.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -30.0000  -60.0000 44

 40 omega   77.00  131.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -90.0000  -82.8062 54

 41 omega   21.00  124.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -61.0000  150.0000 103

 42 omega   60.00  159.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000   60.0000 99

 43 omega    9.00   58.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -90.0000  -82.8062 49

 44 omega   54.00   80.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -55.0000  -36.0000 26

 45 omega   60.00  171.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000 -120.0000 111

 46 omega   60.00   99.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000 -150.0000 39

 47 omega   13.00  127.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -93.0000   76.0221 114

 48 omega   22.00   48.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -55.0000  -36.0000 26

 49 omega  133.00  164.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000 -180.0000 31

 50 omega  131.00  161.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   61.0000  -30.0000 30

 51 omega  100.00  126.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -92.0000  -48.8347 26

 52 omega   61.00  104.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000 -180.0000 43

 53 omega   43.00   69.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -15.0000    0.0000 26

 54 omega   74.00  100.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -15.0000    0.0000 26

 55 omega  126.00  168.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000    0.0000 42

 56 omega   13.00   59.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -92.0000  -48.8347 46

 57 omega  106.00  132.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  125.0000  120.0000 26

 58 omega  139.00  164.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  125.0000  120.0000 25

 59 omega   60.00  105.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000    0.0000 45

 60 omega   92.00  161.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000   90.0000 69

 61 omega   28.00  113.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -61.0000   60.0000 85

 62 omega   72.00  152.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   30.0000 -150.0000 80

 63 omega   68.00  131.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -92.0000  179.2320 63

 64 omega   73.00  148.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   45.0000 -120.0000 75

 65 omega   60.00   87.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000   90.0000 27

 66 omega   60.00  171.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   77.0000  -90.0000 111

 67 omega  116.00  170.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   72.0000   22.6431 54

 68 omega  -99.00  -18.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.9655  125.0000   90.0000 81

 69 omega    8.00  110.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.9655   77.0000  -60.0000 102

 70 omega   24.00  137.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   77.0000  129.1963 113

 71 omega   28.00  142.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   79.0000 -158.2146 114

 72 omega   32.00  146.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   79.0000   -0.4747 114

 73 omega   32.00  146.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   79.0000  -99.9803 114

 74 omega   32.00  146.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   79.0000  -59.7422 114

 75 omega   32.00  145.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   77.0000  140.6230 113

 76 omega   32.00  145.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   77.0000   68.9710 113
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0453515000
_diffrn_orient_matrix_UB_12      -0.1356481000
_diffrn_orient_matrix_UB_13      -0.0480744000
_diffrn_orient_matrix_UB_21      0.0770528000
_diffrn_orient_matrix_UB_22      -0.0177926000
_diffrn_orient_matrix_UB_23      -0.0342331000
_diffrn_orient_matrix_UB_31      0.0442803000
_diffrn_orient_matrix_UB_32      -0.1078758000
_diffrn_orient_matrix_UB_33      0.0661186000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0518
_diffrn_reflns_av_unetI/netI     0.0153
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            65129
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.500
_diffrn_reflns_theta_max         66.780
_diffrn_reflns_theta_min         3.255
_diffrn_source                   'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.537
_exptl_absorpt_correction_T_max  0.827
_exptl_absorpt_correction_T_min  0.691
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.329
_exptl_crystal_F_000             1040
_exptl_crystal_size_max          0.2871
_exptl_crystal_size_mid          0.2849
_exptl_crystal_size_min          0.1359
_refine_diff_density_max         0.317
_refine_diff_density_min         -0.480
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     341
_refine_ls_number_reflns         4373
_refine_ls_number_restraints     345
_refine_ls_restrained_S_all      0.995
_refine_ls_R_factor_all          0.0392
_refine_ls_R_factor_gt           0.0351
_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^)+(0.0479P)^2^+1.5257P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0896
_refine_ls_wR_factor_ref         0.0929
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3952
_reflns_number_total             4373
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5ra00499c2.cif
_cod_data_source_block           mjh140029_fa
_cod_original_cell_volume        2471.70(6)
_cod_database_code               7219494
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C26 H26 N2 O6 S1'
_reflns_odcompleteness_completeness 99.94
_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
2. Restrained distances
 O4B-C17 \\sim O4C-C17 \\sim O4A-C17
 with sigma of 0.01
 O4B-C18B \\sim O4C-C18C \\sim O4A-C18A
 with sigma of 0.01
 C19B-C18B \\sim C19C-C18C \\sim C19A-C18A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C18A) = Uanis(C18C) = Uanis(C18B)
Uanis(C19A) = Uanis(C19C) = Uanis(C19B)
Uanis(O4A) = Uanis(O4C) = Uanis(O4B)
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: O4B(0.18) C18B(0.18) H18A(0.18) H18B(0.18) C19B(0.18) H19A(0.18)
 H19B(0.18) H19C(0.18) O4A(0.4) C18A(0.4) H18C(0.4) H18D(0.4) C19A(0.4)
 H19D(0.4) H19E(0.4) H19F(0.4) O4C(0.42) C18C(0.42) H18E(0.42) H18F(0.42)
 C19C(0.42) H19G(0.42) H19H(0.42) H19I(0.42)
6.a Ternary CH refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11)
6.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C16(H16A,H16B), C18B(H18A,H18B), C18A(H18C,H18D), C18C(H18E,
 H18F)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C12(H12), C21(H21), C22(H22), C24(H24),
 C25(H25)
6.d Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C19B(H19A,H19B,H19C), C19A(H19D,H19E,H19F), C19C(H19G,
 H19H,H19I)
;
_shelx_res_checksum              50469
_olex2_submission_special_instructions 'No special instructions were received'