Transposition of an acrylate moiety in TMSOTf-mediated reaction of alkynyl vinylogous carbonates gives heterocyclic dienes
Gharpure, Santosh J.; Fartade, Dipak J.; Gupta, Krishna S.; Patel, Raj K.; Chemical Communications  (2022) –; doi:10.1039/D2CC03802A

data_7130523
_publ_section_title
;
 Transposition of an acrylate moiety in TMSOTf-mediated reaction of
 alkynyl vinylogous carbonates gives heterocyclic dienes
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC03802A
_journal_year                    2022
_chemical_formula_moiety         'C28 H33 N O5 S'
_chemical_formula_sum            'C28 H33 N O5 S'
_chemical_formula_weight         495.61
_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     dual
_audit_creation_date             2022-03-15
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2022-06-25 deposited with the CCDC.	2022-08-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.570(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.7622(4)
_cell_length_b                   14.0804(3)
_cell_length_c                   16.2304(5)
_cell_measurement_reflns_used    6973
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      24.2360
_cell_measurement_theta_min      1.9190
_cell_volume                     2589.38(14)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_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      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \f    -33.73 174.27   1.00    2.00   6.61  -9.84 -31.50    --   208
  2  \w    -65.46  -0.46   1.00    2.00    --  -19.34  94.56  73.16   65
  3  \w   -100.81  15.19   1.00    2.00    --   -9.84 -59.25-123.92  116
  4  \w    -65.46  -0.46   1.00    2.00    --  -19.34  94.56   1.16   65
  5  \w    -60.88   0.12   1.00    2.00    --  -14.77  94.56 -34.84   61
  6  \w   -100.81  15.19   1.00    2.00    --   -9.84 -59.25  20.08  116
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0524115000
_diffrn_orient_matrix_UB_12      -0.0024058000
_diffrn_orient_matrix_UB_13      0.0136110000
_diffrn_orient_matrix_UB_21      0.0342493000
_diffrn_orient_matrix_UB_22      -0.0037332000
_diffrn_orient_matrix_UB_23      0.0431078000
_diffrn_orient_matrix_UB_31      0.0000258000
_diffrn_orient_matrix_UB_32      0.0501700000
_diffrn_orient_matrix_UB_33      0.0038709000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1015
_diffrn_reflns_av_unetI/netI     0.0451
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            44142
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         1.916
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.163
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90165
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
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    1.271
_exptl_crystal_description       block
_exptl_crystal_F_000             1056
_exptl_crystal_size_max          0.438
_exptl_crystal_size_mid          0.046
_exptl_crystal_size_min          0.023
_refine_diff_density_max         0.322
_refine_diff_density_min         -0.416
_refine_diff_density_rms         0.051
_refine_ls_extinction_coef       0.0071(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     320
_refine_ls_number_reflns         4561
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0611
_refine_ls_R_factor_gt           0.0463
_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^)+(0.0560P)^2^+1.1223P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1153
_refine_ls_wR_factor_ref         0.1255
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3604
_reflns_number_total             4561
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03802a2.cif
_cod_data_source_block           sjg_djf_10_60_s1_autored
_cod_database_code               7130523
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.996
_shelx_estimated_absorpt_t_min   0.932
_reflns_odcompleteness_completeness 82.51
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     36.86
_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:
 C00F(H00F), C00H(H00H)
2.b Secondary CH2 refined with riding coordinates:
 C009(H00A,H00B), C00R(H00C,H00G), C00T(H00M,H00P), C00U(H00R,H00T), C00V(H00U,
 H00V), C00W(H00W,H00X)
2.c Aromatic/amide H refined with riding coordinates:
 C00D(H00D), C00E(H00E), C00I(H00I), C00J(H00J), C00K(H00K), C00L(H00L),
 C00N(H00N), C00O(H00O), C00Q(H00Q), C00S(H00S)
2.d Idealised Me refined as rotating group:
 C00X(H00Y,H,HA), C00Y(H00Z,HB,HC), C00Z(H00,HD,HE)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              25466
_shelx_hkl_checksum              12320
_shelx_fab_checksum              91817
_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 1.221
_oxdiff_exptl_absorpt_empirical_full_min 0.818