α-Regioselective [3 + 2] annulations with Morita‒Baylis‒Hillman carbonates of isatins and 2-nitro-1,3-enynes
Ran, Guang-Yao; Wang, Pan; Du, Wei; Chen, Ying-Chun; Organic Chemistry Frontiers 3 (2016) 861–; doi:10.1039/C6QO00118A

data_1553449
_publ_section_title
;
 \a-Regioselective [3 + 2] annulations with Morita--Baylis--Hillman
 carbonates of isatins and 2-nitro-1,3-enynes
;
_journal_issue                   7
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              861
_journal_paper_doi               10.1039/C6QO00118A
_journal_volume                  3
_journal_year                    2016
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C32 H25 N O5.95'
_chemical_formula_sum            'C32 H25 N O6'
_chemical_formula_weight         519.53
_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
_atom_sites_solution_primary     direct
_audit_creation_date             2016-03-23
_audit_creation_method
;
Olex2 1.2
(compiled 2014.06.23 svn.r2946 for OlexSys, GUI svn.r4855)
;
_audit_update_record
;
2016-03-24 deposited with the CCDC.
2016-05-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.02156(13)
_cell_length_b                   9.44417(11)
_cell_length_c                   30.9480(4)
_cell_measurement_reflns_used    10392
_cell_measurement_temperature    291.29(10)
_cell_measurement_theta_max      71.4350
_cell_measurement_theta_min      4.3130
_cell_volume                     2636.81(6)
_computing_cell_refinement
'CrysAlisPro, Agilent Technologies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET) (compiled May 22 2014,16:03:01)'
_computing_data_collection
'CrysAlisPro, Agilent Technologies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET) (compiled May 22 2014,16:03:01)'
_computing_data_reduction
'CrysAlisPro, Agilent Technologies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET) (compiled May 22 2014,16:03:01)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      291.29(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0243
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_details
;
  1 omega    7.00  108.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7203   19.0000 -180.0000 101

  2 omega   10.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7203   77.0000 -180.0000 94

  3 omega    1.00   76.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7203  -99.0000  -30.0000 75

  4 omega  -31.00   53.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7203  -57.0000   60.0000 84

  5 omega   40.00   98.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  120.0000 58

  6 omega   38.00  116.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -112.0000  -30.0000 78

  7 omega   38.00   91.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -60.0000 53

  8 omega   39.00  110.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -95.0000  150.0000 71

  9 omega   38.00   91.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -90.0000 53

 10 omega   38.00   91.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -150.0000 53

 11 omega   38.00   91.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -120.0000 53

 12 omega   40.00   98.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -90.0000 58

 13 omega   -2.00  108.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7203   15.0000   61.0000 110

 14 omega   10.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7203   77.0000  -90.0000 94

 15 omega   55.00  109.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7203 -178.0000  -60.0000 54

 16 omega   70.00  178.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000  -60.0000 108
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0321871000
_diffrn_orient_matrix_UB_12      0.0634661000
_diffrn_orient_matrix_UB_13      0.0448761000
_diffrn_orient_matrix_UB_21      0.0170455000
_diffrn_orient_matrix_UB_22      -0.1477600000
_diffrn_orient_matrix_UB_23      0.0204445000
_diffrn_orient_matrix_UB_31      0.1668160000
_diffrn_orient_matrix_UB_32      0.0273561000
_diffrn_orient_matrix_UB_33      0.0065506000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0290
_diffrn_reflns_av_unetI/netI     0.0224
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            13769
_diffrn_reflns_point_group_measured_fraction_full 0.922
_diffrn_reflns_point_group_measured_fraction_max 0.897
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.377
_diffrn_reflns_theta_min         4.896
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.742
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48107
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro, Agilent Technologies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET) (compiled May 22 2014,16:03:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_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    1.309
_exptl_crystal_description       block
_exptl_crystal_F_000             1088
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.459
_refine_diff_density_min         -0.308
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details
;
 Flack x determined using 1672 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.06(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     355
_refine_ls_number_reflns         4592
_refine_ls_number_restraints     112
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0536
_refine_ls_R_factor_gt           0.0532
_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^)+(0.1089P)^2^+0.8579P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1478
_refine_ls_wR_factor_ref         0.1485
_reflns_Friedel_coverage         0.592
_reflns_Friedel_fraction_full    0.818
_reflns_Friedel_fraction_max     0.781
_reflns_number_gt                4525
_reflns_number_total             4592
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6qo00118a2.cif
_cod_data_source_block           3s
_cod_database_code               1553449
_shelxl_version_number           2014-1
_chemical_oxdiff_formula         'C1 H1 N1 O1'
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.008 and sigma for 1-3 distances of 0.007
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.007
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.007 and sigma for 1-3 distances of 0.007
3. Uiso/Uaniso restraints and constraints
O36: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.01
C35: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.01
C35 \\sim O36: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.02
C35 \\sim O36: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
4.a Ternary CH refined with riding coordinates:
 C10(H10)
4.b Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B)
4.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C3(H3), C6(H6), C5(H5), C15(H15), C4(H4), C17(H17), C19(H19),
 C26(H26), C18(H18), C30(H30), C16(H16), C24(H24), C29(H29), C27(H27), C28(H28)
4.d Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C39(H39A,H39B,H39C)
;
_shelx_res_checksum              91912
_shelx_hkl_checksum              73690
_olex2_submission_special_instructions 'No special instructions were received'