Solvent-controlled nucleophilic trifluoromethylthiolation of Morita–Baylis–Hillman carbonates: dual roles of DABCO in activating the Zard's trifluoromethylthiolation reagent and the MBH carbonates
Yang, Hai-Bin; Fan, Xing; Wei, Yin; Shi, Min; Organic Chemistry Frontiers 2 (2015) 1088–; doi:10.1039/C5QO00198F

data_1553162
_publ_section_title
;
 Solvent-controlled nucleophilic trifluoromethylthiolation of
 Morita--Baylis--Hillman carbonates: dual roles of DABCO in activating the
 Zard's trifluoromethylthiolation reagent and the MBH carbonates
;
_journal_issue                   9
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              1088
_journal_paper_doi               10.1039/C5QO00198F
_journal_volume                  2
_journal_year                    2015
_chemical_formula_moiety         'C10 H9 F3 O2 S2'
_chemical_formula_sum            'C10 H9 F3 O2 S2'
_chemical_formula_weight         282.29
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-01-27
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_audit_update_record
;
2015-02-10 deposited with the CCDC.
2015-07-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.2830(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4647(7)
_cell_length_b                   5.7312(5)
_cell_length_c                   22.1678(18)
_cell_measurement_reflns_used    5942
_cell_measurement_temperature    130
_cell_measurement_theta_max      30.520
_cell_measurement_theta_min      2.526
_cell_volume                     1183.16(17)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0171
_diffrn_reflns_av_unetI/netI     0.0181
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            11335
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.522
_diffrn_reflns_theta_min         1.867
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.475
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6875
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0414 before and 0.0310 after correction.
The Ratio of minimum to maximum transmission is 0.9215.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.585
_exptl_crystal_description       block
_exptl_crystal_F_000             576
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         1.962
_refine_diff_density_min         -1.421
_refine_diff_density_rms         0.140
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     155
_refine_ls_number_reflns         3606
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.0717
_refine_ls_R_factor_gt           0.0645
_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^)+(0.1152P)^2^+2.2469P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1972
_refine_ls_wR_factor_ref         0.2047
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3105
_reflns_number_total             3606
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5qo00198f2.cif
_cod_data_source_block           mo_dm15091_0m
_cod_database_code               1553162
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.919
_shelx_estimated_absorpt_t_min   0.891
_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. Restrained distances
 C3-C4
 1.35 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C3) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B)
4.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C5(H5)
4.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C)
;
_shelx_res_checksum              79492
_shelx_hkl_checksum              22977
_olex2_submission_special_instructions 'No special instructions were received'