Rhodium-catalyzed arylative cyclization of alkynyl malonates by 1,4-rhodium(I) migration
O'Brien, Luke; Karad, Somnath Narayan; Lewis, William; Lam, Hon Wai; Chemical Communications  (2019) –; doi:10.1039/C9CC05205D

data_7124062
_publ_section_title
;
 Rhodium-catalyzed arylative cyclization of alkynyl malonates by
 1,4-rhodium(I) migration
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC05205D
_journal_year                    2019
_chemical_formula_moiety         'C28 H21 F3 O5'
_chemical_formula_sum            'C28 H21 F3 O5'
_chemical_formula_weight         494.45
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2018-06-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-07-04 deposited with the CCDC.    2019-08-19 downloaded from the CCDC.
;
_cell_angle_alpha                97.3475(16)
_cell_angle_beta                 91.0050(17)
_cell_angle_gamma                112.494(2)
_cell_formula_units_Z            2
_cell_length_a                   9.9782(2)
_cell_length_b                   10.9927(2)
_cell_length_c                   11.6441(2)
_cell_measurement_reflns_used    10736
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      77.0660
_cell_measurement_theta_min      4.7810
_cell_volume                     1167.27(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_type            'PILATUS3 R 200K Hybrid Pixel Array Detector'
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.954
_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    -33.00  18.00   0.50    0.50    --    0.00 -82.00   0.00  102
  2  \w    -30.00  31.00   0.50    0.50    --    0.00 -82.00 120.00  122
  3  \w    -23.00  17.00   0.50    0.50    --    0.00  38.00 -90.00   80
  4  \w    -31.00  21.00   0.50    0.50    --    0.00 -82.00 -60.00  104
  5  \w     36.00  88.00   0.50    0.50    --    0.00  38.00 -90.00  104
  6  \w     19.00  47.00   0.50    0.50    --  102.40 -30.00  90.00   56
  7  \w     20.00  68.00   0.50    0.50    --  102.40 -30.00 120.00   96
  8  \w     17.00  94.00   0.50    0.50    --  102.40 -82.00  60.00  154
  9  \w     33.00  77.00   0.50    0.50    --  102.40 -45.00-180.00   88
 10  \w     19.00 127.00   0.50    0.50    --  102.40 -82.00-150.00  216
 11  \w     60.00 135.00   0.50    0.50    --  102.40 -82.00  90.00  150
 12  \w     13.00  72.00   0.50    0.50    --  102.40 -45.00-120.00  118
 13  \w     17.00  70.00   0.50    0.50    --  102.40 -45.00 -30.00  106
 14  \w     19.00 109.00   0.50    0.50    --  102.40 -82.00 120.00  180
 15  \w     80.00 115.00   0.50    0.50    --  102.40 -82.00-180.00   70
 16  \w     77.00 134.00   0.50    0.50    --  102.40 -77.00 -60.00  114
 17  \w     61.00 101.00   0.50    0.50    --  102.40 -82.00   0.00   80
 18  \w     30.00 100.00   0.50    0.50    --  102.40 -82.00 -90.00  140
 19  \w     38.00  67.00   0.50    0.50    --  102.40 -77.00 -60.00   58
 20  \w     18.00  72.00   0.50    0.50    --  102.40 -77.00 150.00  108
 21  \w    101.00 130.00   0.50    0.50    --  102.40 -77.00 150.00   58
 22  \w     14.00  41.00   0.50    0.50    --  102.40 -82.00  90.00   54
 23  \w     25.00  50.00   0.50    0.50    --  102.40 -82.00-180.00   50
 24  \w     21.00  69.00   0.50    0.50    --  102.40 -30.00 -90.00   96
 25  \w     13.00  67.00   0.50    0.50    --  102.40 -30.00 -30.00  108
 26  \w     94.00 129.00   0.50    0.50    --  102.40 -82.00-120.00   70
 27  \w     24.00  52.00   0.50    0.50    --  102.40 -77.00  90.00   56
 28  \w     80.00 105.00   0.50    0.50    --  102.40 -77.00  90.00   50
 29  \w     35.00  66.00   0.50    0.50    --  102.40 -45.00 -60.00   62
 30  \w    104.00 130.00   0.50    0.50    --  102.40 -77.00 -90.00   52
 31  \w     21.00 132.00   0.50    0.50    --  102.40 -15.00 150.00  222
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'XtalLAB PRO MM007, PILATUS3 R 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1341161000
_diffrn_orient_matrix_UB_12      0.0345242000
_diffrn_orient_matrix_UB_13      -0.0171366000
_diffrn_orient_matrix_UB_21      0.0951560000
_diffrn_orient_matrix_UB_22      0.1267628000
_diffrn_orient_matrix_UB_23      -0.0486932000
_diffrn_orient_matrix_UB_31      -0.0320990000
_diffrn_orient_matrix_UB_32      -0.0790347000
_diffrn_orient_matrix_UB_33      -0.1233894000
_diffrn_radiation_collimation    'VariMax VHF mirror optic'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_wavelength_determination fundamental
_diffrn_reflns_av_R_equivalents  0.0175
_diffrn_reflns_av_unetI/netI     0.0151
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            12621
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.386
_diffrn_reflns_theta_min         3.838
_diffrn_source                   'rotating anode'
_diffrn_source_current           30
_diffrn_source_power             1.2
_diffrn_source_target            Cu
_diffrn_source_type              'MicroMax 007 HF'
_diffrn_source_voltage           40
_exptl_absorpt_coefficient_mu    0.950
_exptl_absorpt_correction_T_max  0.853
_exptl_absorpt_correction_T_min  0.716
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.407
_exptl_crystal_description       block
_exptl_crystal_F_000             512
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: dichloromethane and petroleum ether'
_exptl_crystal_size_max          0.606
_exptl_crystal_size_mid          0.394
_exptl_crystal_size_min          0.236
_refine_diff_density_max         0.252
_refine_diff_density_min         -0.219
_refine_diff_density_rms         0.043
_refine_ls_extinction_coef       0.0108(5)
_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   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     326
_refine_ls_number_reflns         4729
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0360
_refine_ls_R_factor_gt           0.0347
_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^)+(0.0456P)^2^+0.4012P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0903
_refine_ls_wR_factor_ref         0.0913
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4533
_reflns_number_total             4729
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc05205d2.cif
_cod_data_source_block           lobhla
_cod_original_cell_volume        1167.26(5)
_cod_database_code               7124062
_nottingham_internal_coll_name   LOBHLA
_nottingham_internal_coll_number 17730
_nottingham_internal_coll_client LOB/HWL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time 0.50
_nottingham_internal_coll_frame_width 0.50
_nottingham_internal_coll_user   pczwl
_nottingham_internal_coll_date   13/06/2018
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'XtalLAB PRO, A00000876'
_nottingham_internal_process_date 13/06/2018
_nottingham_internal_process_user pczwl
_nottingham_internal_solution_date 13/6/2018
_nottingham_internal_solution_user pczwl
_nottingham_internal_refinement_date 13/6/2018
_nottingham_internal_refinement_user pczwl
_nottingham_internal_validation_date 15/6/2018
_nottingham_internal_validation_user pczwl
_nottingham_internal_archive_date 15/6/2018
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C28 H21 F3 O5'
_chemical_oxdiff_usercomment
'LOBHLA #17730 MM-669 IN FOMLBIN FILM ON A MICROMOUNT FOR LOB/HWL'
_reflns_odcompleteness_completeness 98.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C14(H14A,H14B), C19(H19A,H19B)
2.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C24(H24), C25(H25), C26(H26), C27(H27),
 C28(H28), C29(H29), C31(H31), C32(H32), C33(H33), C34(H34), C35(H35)
;
_shelx_res_checksum              93877
_olex2_date_sample_data_collection 2018-06-13
_olex2_date_sample_submission    2018-06-12
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_original_sample_id LOB_233
_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 1.490
_oxdiff_exptl_absorpt_empirical_full_min 0.593