Tandem Rh(ii)-catalyzed 1,3-acyloxy migration/intermolecular [2 + 2] cycloaddition of electron-deficient propargylic esters with alkenes and alkynes.
Xu, Zurong; Zhu, Dong; Wu, Rui; Zhu, Shifa; Chemical science 16 (2024) 205–210; doi:10.1039/d4sc06458e

data_1573214
_publ_section_title
;
 Tandem Rh(ii)-catalyzed 1,3-acyloxy migration/intermolecular [2 + 2]
 cycloaddition of electron-deficient propargylic esters with alkenes and
 alkynes.
;
_journal_issue                   1
_journal_name_full               'Chemical science'
_journal_page_first              205
_journal_page_last               210
_journal_paper_doi               10.1039/d4sc06458e
_journal_volume                  16
_journal_year                    2024
_chemical_formula_moiety         'C14 H13 Br O3'
_chemical_formula_sum            'C14 H13 Br O3'
_chemical_formula_weight         309.15
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2023-04-01
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2024-02-27 deposited with the CCDC.	2024-11-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.115(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.5459(6)
_cell_length_b                   7.4134(4)
_cell_length_c                   27.118(3)
_cell_measurement_reflns_used    2753
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      70.9200
_cell_measurement_theta_min      3.2270
_cell_volume                     1308.5(2)
_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 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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   -117.00  -8.00   1.00    1.00    --  -40.92 -77.00   0.00  109
  2  \w   -115.00 -17.00   1.00    1.00    --  -40.92 -37.00-150.00   98
  3  \w     23.00  97.00   1.00    1.00    --   40.92-125.00  30.00   74
  4  \w     17.00  92.00   1.00    1.00    --   40.92-117.00-150.00   75
  5  \w     17.00 115.00   1.00    1.00    --   40.92  37.00 120.00   98
  6  \w     81.00 178.00   1.00    1.50    --  106.95  45.00 -90.00   97
  7  \w     34.00 121.00   1.00    1.50    --  106.95-125.00 150.00   87
  8  \w     32.00  74.00   1.00    1.50    --  106.95 -15.00-150.00   42
  9  \w     42.00  86.00   1.00    1.50    --  106.95 -30.00 -60.00   44
 10  \w    100.00 135.00   1.00    1.50    --  106.95 -30.00 120.00   35
 11  \w    106.00 134.00   1.00    1.50    --  106.95 -30.00 -60.00   28
 12  \w    126.00 178.00   1.00    1.50    --  106.95 125.00  30.00   52
 13  \w     32.00  95.00   1.00    1.50    --  106.95 -30.00 120.00   63
 14  \w     81.00 149.00   1.00    1.50    --  106.95  45.00 120.00   68
 15  \w     87.00 144.00   1.00    1.50    --  106.95 -15.00-150.00   57
 16  \w     35.00 136.00   1.00    1.50    --  106.95 -61.00 120.00  101
 17  \w     82.00 109.00   1.00    1.50    --  106.95 -94.00 -60.00   27
 18  \w     32.00 140.00   1.00    1.50    --  106.95 -77.00 -60.00  108
;
_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      0.0742923000
_diffrn_orient_matrix_UB_12      0.0579478000
_diffrn_orient_matrix_UB_13      0.0535210000
_diffrn_orient_matrix_UB_21      0.0124809000
_diffrn_orient_matrix_UB_22      0.1972671000
_diffrn_orient_matrix_UB_23      -0.0172792000
_diffrn_orient_matrix_UB_31      -0.2242336000
_diffrn_orient_matrix_UB_32      0.0301412000
_diffrn_orient_matrix_UB_33      0.0102624000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.1447
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -3
_diffrn_reflns_number            2308
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        66.568
_diffrn_reflns_theta_max         66.568
_diffrn_reflns_theta_min         3.278
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.273
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48611
_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            'light colourless'
_exptl_crystal_density_diffrn    1.569
_exptl_crystal_description       prism
_exptl_crystal_F_000             624
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.08
_refine_diff_density_max         3.426
_refine_diff_density_min         -1.543
_refine_diff_density_rms         0.439
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   2.595
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     165
_refine_ls_number_reflns         2308
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      2.595
_refine_ls_R_factor_all          0.1251
_refine_ls_R_factor_gt           0.1137
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3452
_refine_ls_wR_factor_ref         0.3523
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1980
_reflns_number_total             2308
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc06458e2.cif
_cod_data_source_block           2_211_1
_cod_depositor_comments
'Adding full bibliography for 1573214--1573215.cif.'
_cod_original_cell_volume        1308.48(19)
_cod_database_code               1573214
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.726
_shelx_estimated_absorpt_t_min   0.607
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.712(7)
 0.288(7)
2. 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
3.a Ternary CH refined with riding coordinates:
 C7(H7)
3.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C10(H10A,H10B)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C11(H11)
3.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C)
;
_shelx_res_checksum              2077
_shelx_hkl_checksum              17862
_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 1.662
_oxdiff_exptl_absorpt_empirical_full_min 0.683