Chiral Brønsted Acid Catalyzed Enantioselective Dehydrative Nazarov-Type Electrocyclization of Aryl and 2-Thienyl Vinyl Alcohols.
Jin, Jianwen; Zhao, Yichao; Gouranourimi, Ali; Ariafard, Alireza; Hong Chan, Philip Wai; Journal of the American Chemical Society 140 (2018) 5834–5841; doi:10.1021/jacs.8b02339

data_4132196
_publ_section_title
;
 Chiral Br\/onsted Acid Catalyzed Enantioselective Dehydrative
 Nazarov-Type Electrocyclization of Aryl and 2-Thienyl Vinyl Alcohols.
;
_journal_issue                   17
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5834
_journal_page_last               5841
_journal_paper_doi               10.1021/jacs.8b02339
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C31 H25 N O3 S'
_chemical_formula_sum            'C31 H25 N O3 S'
_chemical_formula_weight         491.58
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-01-30
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.62577(3)
_cell_length_b                   14.48480(7)
_cell_length_c                   18.25680(7)
_cell_measurement_reflns_used    25347
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.4770
_cell_measurement_theta_min      4.5510
_cell_volume                     2545.497(18)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3046
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -66.00  33.00   1.00    1.25    --  -41.82  37.00  90.00   99
  2  \w    -66.00  33.00   1.00    1.25    --  -41.82  37.00-180.00   99
  3  \w     94.00 178.00   1.00    5.00    --  107.00 125.00 120.00   84
  4  \w     94.00 178.00   1.00    5.00    --  107.00 125.00 -90.00   84
  5  \w     81.00 178.00   1.00    5.00    --  107.00  45.00-180.00   97
  6  \w     94.00 178.00   1.00    5.00    --  107.00 125.00   0.00   84
  7  \w     24.00 109.00   1.00    5.00    --  107.00 -94.00  60.00   85
  8  \w   -116.00 -17.00   1.00    1.25    --  -41.82 -37.00  60.00   99
  9  \w   -114.00 -14.00   1.00    1.25    --  -41.82 -57.00 -30.00  100
 10  \w     81.00 178.00   1.00    5.00    --  107.00  45.00  90.00   97
 11  \w     74.00 178.00   1.00    5.00    --  107.00  77.00-150.00  104
 12  \w     74.00 178.00   1.00    5.00    --  107.00  77.00   0.00  104
 13  \w     54.00 178.00   1.00    5.00    --  107.00  15.00 -30.00  124
 14  \w   -114.00 -14.00   1.00    1.25    --  -41.82 -57.00-180.00  100
 15  \w     23.00  98.00   1.00    1.25    --   41.82-125.00 -30.00   75
 16  \w     34.00 121.00   1.00    5.00    --  107.00-125.00 -30.00   87
 17  \w     74.00 178.00   1.00    5.00    --  107.00  77.00 -30.00  104
 18  \w     74.00 178.00   1.00    5.00    --  107.00  77.00  30.00  104
 19  \w     78.00 178.00   1.00    5.00    --  107.00  61.00 120.00  100
 20  \w   -118.00 -41.00   1.00    1.25    --  -41.82 -77.00 -90.00   77
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0587169000
_diffrn_orient_matrix_UB_12      0.0477903000
_diffrn_orient_matrix_UB_13      0.0687596000
_diffrn_orient_matrix_UB_21      -0.1486008000
_diffrn_orient_matrix_UB_22      -0.0240690000
_diffrn_orient_matrix_UB_23      -0.0247503000
_diffrn_orient_matrix_UB_31      0.0084534000
_diffrn_orient_matrix_UB_32      -0.0919022000
_diffrn_orient_matrix_UB_33      0.0422533000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0178
_diffrn_reflns_av_unetI/netI     0.0103
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            30136
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.649
_diffrn_reflns_theta_min         3.896
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.392
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79597
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.283
_exptl_crystal_description       block
_exptl_crystal_F_000             1032
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.227
_refine_diff_density_min         -0.261
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 2157 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Hooft y: -0.010(2) Olex2 
Flack x: -0.002(3) Shelx 2016
;
_refine_ls_abs_structure_Flack   -0.002(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     330
_refine_ls_number_reflns         5077
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0251
_refine_ls_R_factor_gt           0.0250
_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^)+(0.0450P)^2^+0.3263P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0698
_refine_ls_wR_factor_ref         0.0699
_reflns_Friedel_coverage         0.757
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.981
_reflns_number_gt                5043
_reflns_number_total             5077
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b02339_si_002.cif
_cod_data_source_block           dd16
_cod_original_cell_volume        2545.496(17)
_cod_database_code               4132196
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C20 H20 N2 O2 S'
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_olex2_refinement_description
;
The NH was located in a difference map and allowed to refine freely but given a Uiso 1.2 times 
the Uequiv of the parent nitrogen.

1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C11(H11)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C13(H13), C15(H15), C16(H16), C22(H22),
 C23(H23), C24(H24), C25(H25), C26(H26), C28(H28), C29(H29), C30(H30), C31(H31),
  C32(H32)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C33(H33A,H33B,H33C)
;
_shelx_res_checksum              10637
_shelx_hkl_checksum              48980
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.326
_oxdiff_exptl_absorpt_empirical_full_min 0.815