Diastereoselective B(C6F5)3-Catalyzed Reductive Carbocyclization of Unsaturated Carbohydrates.
Bender, Trandon A.; Dabrowski, Jennifer A.; Zhong, Hongyu; Gagné, Michel R; Organic letters 18 (2016) 4120–4123; doi:10.1021/acs.orglett.6b02050

data_1555681
_publ_section_title
;
 Diastereoselective B(C6F5)3-Catalyzed Reductive Carbocyclization of
 Unsaturated Carbohydrates.
;
_journal_issue                   16
_journal_name_full               'Organic letters'
_journal_page_first              4120
_journal_page_last               4123
_journal_paper_doi               10.1021/acs.orglett.6b02050
_journal_volume                  18
_journal_year                    2016
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C27 H23 Br N2 O8, 0.5(C H Cl3)'
_chemical_formula_sum            'C27.5 H23.5 Br Cl1.5 N2 O8'
_chemical_formula_weight         643.07
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-12-17
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                73.497(2)
_cell_angle_beta                 87.912(2)
_cell_angle_gamma                72.630(2)
_cell_formula_units_Z            2
_cell_length_a                   9.4486(3)
_cell_length_b                   11.0765(3)
_cell_length_c                   16.0570(5)
_cell_measurement_reflns_used    8115
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      66.65
_cell_measurement_theta_min      4.37
_cell_volume                     1535.63(8)
_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_temperature      100.15
_diffrn_measured_fraction_theta_full 0.966
_diffrn_measured_fraction_theta_max 0.966
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0458
_diffrn_reflns_av_unetI/netI     0.0545
_diffrn_reflns_Laue_measured_fraction_full 0.966
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            24104
_diffrn_reflns_point_group_measured_fraction_full 0.909
_diffrn_reflns_point_group_measured_fraction_max 0.909
_diffrn_reflns_theta_full        66.797
_diffrn_reflns_theta_max         66.797
_diffrn_reflns_theta_min         4.365
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.442
_exptl_absorpt_correction_T_max  0.7430
_exptl_absorpt_correction_T_min  0.3576
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0786 before and 0.0606 after correction.
The Ratio of minimum to maximum transmission is 0.4813.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.391
_exptl_crystal_description       block
_exptl_crystal_F_000             654
_exptl_crystal_recrystallization_method
'Slow diffusion of pentanes and chloroform at -24 degrees celsius over 1 week'
_exptl_crystal_size_max          0.411
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.101
_refine_diff_density_max         1.000
_refine_diff_density_min         -0.516
_refine_diff_density_rms         0.061
_refine_ls_abs_structure_details
;
 Flack x determined using 3354 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.034(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     723
_refine_ls_number_reflns         9926
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0549
_refine_ls_R_factor_gt           0.0462
_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^)+(0.0705P)^2^+0.0476P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1161
_refine_ls_wR_factor_ref         0.1215
_reflns_Friedel_coverage         0.882
_reflns_Friedel_fraction_full    0.852
_reflns_Friedel_fraction_max     0.852
_reflns_number_gt                8400
_reflns_number_total             9926
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b02050_si_003.cif
_cod_data_source_block           x1511011
_cod_original_formula_sum        'C27.50 H23.50 Br Cl1.50 N2 O8'
_cod_database_code               1555681
_shelx_estimated_absorpt_t_max   0.723
_shelx_estimated_absorpt_t_min   0.332
_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.a Ternary CH refined with riding coordinates:
 C4A(H4A), C2A(H2A), C5A(H5A), C6A(H6A), C6(H6), C2(H2), C4(H4), C5(H5),
 C28(H28)
2.b Secondary CH2 refined with riding coordinates:
 C1A(H1AA,H1AB), C7A(H7AA,H7AB), C1(H1A,H1B), C7(H7A,H7B)
2.c Aromatic/amide H refined with riding coordinates:
 C13A(H13A), C12A(H12A), C10A(H10A), C9A(H9A), C20A(H20A), C19A(H19A),
 C17A(H17A), C16A(H16A), C23A(H23A), C24A(H24A), C26A(H26A), C27A(H27A),
 C13(H13), C12(H12), C10(H10), C9(H9), C20(H20), C19(H19), C17(H17), C16(H16),
 C23(H23), C24(H24), C26(H26), C27(H27)
2.d Idealised Me refined as rotating group:
 C3A(H3AA,H3AB,H3AC), C3(H3A,H3B,H3C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'