Catalytic enantioselective arylative cyclizations of alkynyl 1,3-diketones by 1,4-rhodium(i) migration
Groves, Alistair; Sun, Jinwei; Parke, Hal R. I.; Callingham, Michael; Argent, Stephen P.; Taylor, Laurence J.; Lam, Hon Wai; Chemical Science 11 (2020) 2759–2764; doi:10.1039/C9SC06309A

data_1557262
_publ_section_title
;
 Catalytic enantioselective arylative cyclizations of alkynyl
 1,3-diketones by 1,4-rhodium(i) migration
;
_journal_issue                   10
_journal_name_full               'Chemical Science'
_journal_page_first              2759
_journal_page_last               2764
_journal_paper_doi               10.1039/C9SC06309A
_journal_volume                  11
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H21 F O2'
_chemical_formula_sum            'C21 H21 F O2'
_chemical_formula_weight         324.38
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-07-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-10-17 deposited with the CCDC.	2020-02-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.502(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.5120(2)
_cell_length_b                   15.3360(3)
_cell_length_c                   8.7541(2)
_cell_measurement_reflns_used    24403
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      74.2730
_cell_measurement_theta_min      2.8630
_cell_volume                     813.41(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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 10.3613
_diffrn_detector_type            'Agilent Diffraction Atlas detector'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.995
_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    -50.00  34.00   1.00    1.00    --  -38.50  38.00  90.00   84
  2  \w    -93.00  -2.00   1.00    1.00    --  -38.50 125.00 -60.00   91
  3  \w      1.00  83.00   1.00    1.00    --   43.32 -99.00 -30.00   82
  4  \w     31.00  91.00   1.00    4.00    --  106.13 -30.00-150.00   60
  5  \w     25.00 109.00   1.00    4.00    --  106.13 -95.00 120.00   84
  6  \w     31.00  91.00   1.00    4.00    --  106.13 -30.00  60.00   60
  7  \w     25.00 109.00   1.00    4.00    --  106.13 -95.00   0.00   84
  8  \w     35.00 117.00   1.00    4.00    --  106.13-125.00 -30.00   82
  9  \w     82.00 177.00   1.00    4.00    --  106.13  45.00 120.00   95
 10  \w     17.00 113.00   1.00    1.00    --   43.32  57.00  60.00   96
 11  \w     17.00 113.00   1.00    1.00    --   43.32  57.00 -60.00   96
 12  \w     79.00 176.00   1.00    4.00    --  106.13  61.00   0.00   97
 13  \w     61.00 178.00   1.00    4.00    --  106.13  15.00 -30.00  117
 14  \w     79.00 176.00   1.00    4.00    --  106.13  61.00  60.00   97
 15  \w     82.00 178.00   1.00    4.00    --  106.13  30.00-150.00   96
 16  \w    -50.00  28.00   1.00    1.00    --  -38.50  38.00-150.00   78
 17  \w     17.00 113.00   1.00    1.00    --   43.32  57.00-180.00   96
 18  \w     61.00  87.00   1.00    1.00    --   43.38  38.00 120.00   26
 19  \w     91.00 116.00   1.00    1.00    --   43.38  38.00 120.00   25
 20  \w    144.00 170.00   1.00    4.00    --  106.13  61.00  90.00   26
 21  \w     79.00 105.00   1.00    4.00    --  106.13  61.00  90.00   26
 22  \w     61.00 106.00   1.00    4.00    --  106.13 -61.00 120.00   45
 23  \w     95.00 132.00   1.00    4.00    --  106.13  30.00 150.00   37
 24  \w    137.00 165.00   1.00    4.00    --  106.13 125.00   0.00   28
 25  \w     97.00 123.00   1.00    4.00    --  106.13 125.00   0.00   26
 26  \w   -112.00  -7.00   1.00    1.00    --  -38.50 -77.00  90.00  105
 27  \w     21.00 116.00   1.00    1.00    --   43.38  38.00 -60.00   95
 28  \w     12.00 117.00   1.00    1.00    --   43.38  77.00-150.00  105
 29  \w     12.00 117.00   1.00    1.00    --   43.38  77.00  90.00  105
 30  \w     23.00  98.00   1.00    1.00    --   43.38-125.00-120.00   75
 31  \w    -29.00  66.00   1.00    1.00    --   43.38 -38.00  30.00   95
 32  \w     12.00 117.00   1.00    1.00    --   43.38  77.00 -30.00  105
 33  \w     79.00 176.00   1.00    4.00    --  106.13  61.00 -90.00   97
 34  \w     25.00 109.00   1.00    4.00    --  106.13 -95.00-150.00   84
 35  \w     79.00 176.00   1.00    4.00    --  106.13  61.00  30.00   97
 36  \w     75.00 178.00   1.00    4.00    --  106.13  77.00 -60.00  103
 37  \w     75.00 178.00   1.00    4.00    --  106.13  77.00 150.00  103
 38  \w     79.00 176.00   1.00    4.00    --  106.13  61.00 150.00   97
 39  \w     75.00 178.00   1.00    4.00    --  106.13  77.00-180.00  103
 40  \w     79.00 176.00   1.00    4.00    --  106.13  61.00-120.00   97
 41  \w     75.00 178.00   1.00    4.00    --  106.13  77.00-150.00  103
 42  \w     79.00 176.00   1.00    4.00    --  106.13  61.00 -60.00   97
 43  \w     75.00 178.00   1.00    4.00    --  106.13  77.00 -30.00  103
 44  \w     79.00 176.00   1.00    4.00    --  106.13  61.00 120.00   97
 45  \w     75.00 178.00   1.00    4.00    --  106.13  77.00  60.00  103
 46  \w     35.00  98.00   1.00    4.00    --  106.13 -45.00 -30.00   63
 47  \w    -75.00  40.00   1.00    1.00    --  -38.50  19.00 -30.00  115
 48  \w    -43.00 130.00   1.00    1.00    --   43.38   0.00-150.00  173
 49  \w     12.00 117.00   1.00    1.00    --   43.38  77.00   0.00  105
 50  \w    -43.00 130.00   1.00    1.00    --   43.38   0.00-180.00  173
 51  \w    -43.00 130.00   1.00    1.00    --   43.38   0.00 -90.00  173
 52  \w    -43.00 130.00   1.00    1.00    --   43.38   0.00-120.00  173
 53  \w     21.00 116.00   1.00    1.00    --   43.38  38.00   0.00   95
 54  \w     82.00 177.00   1.00    4.00    --  106.13  45.00-120.00   95
 55  \w     75.00 178.00   1.00    4.00    --  106.13  77.00  90.00  103
 56  \w     79.00 176.00   1.00    4.00    --  106.13  61.00 -30.00   97
 57  \w     35.00 117.00   1.00    4.00    --  106.13-125.00 120.00   82
 58  \w     82.00 177.00   1.00    4.00    --  106.13  45.00 -30.00   95
 59  \w     75.00 178.00   1.00    4.00    --  106.13  77.00 120.00  103
 60  \w     79.00 176.00   1.00    4.00    --  106.13  61.00-180.00   97
 61  \w     82.00 177.00   1.00    4.00    --  106.13  45.00 150.00   95
 62  \w     75.00 178.00   1.00    4.00    --  106.13  77.00  30.00  103
 63  \w     75.00 178.00   1.00    4.00    --  106.13  77.00-120.00  103
 64  \w     82.00 177.00   1.00    4.00    --  106.13  45.00 -60.00   95
 65  \w     75.00 178.00   1.00    4.00    --  106.13  77.00 -90.00  103
 66  \w     82.00 177.00   1.00    4.00    --  106.13  45.00   0.00   95
 67  \w     75.00 178.00   1.00    4.00    --  106.13  77.00   0.00  103
 68  \w    -43.00  84.00   1.00    1.00    --   43.38   0.00 -60.00  127
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Atlas'
_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      0.0309232000
_diffrn_orient_matrix_UB_12      0.0089661000
_diffrn_orient_matrix_UB_13      0.1823973000
_diffrn_orient_matrix_UB_21      -0.1682928000
_diffrn_orient_matrix_UB_22      -0.0737634000
_diffrn_orient_matrix_UB_23      -0.0198384000
_diffrn_orient_matrix_UB_31      0.1881130000
_diffrn_orient_matrix_UB_32      -0.0675807000
_diffrn_orient_matrix_UB_33      0.0459263000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0213
_diffrn_reflns_av_unetI/netI     0.0074
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            32574
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.496
_diffrn_reflns_theta_min         5.431
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    0.740
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.393
_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            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.324
_exptl_crystal_description       block
_exptl_crystal_F_000             344
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: pentane/dichloromethane'
_exptl_crystal_size_max          0.496
_exptl_crystal_size_mid          0.443
_exptl_crystal_size_min          0.219
_refine_diff_density_max         0.186
_refine_diff_density_min         -0.211
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 1567 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.028(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     223
_refine_ls_number_reflns         3270
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0283
_refine_ls_R_factor_gt           0.0283
_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^)+(0.0482P)^2^+0.1303P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0735
_refine_ls_wR_factor_ref         0.0735
_reflns_Friedel_coverage         0.922
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                3269
_reflns_number_total             3270
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc06309a2.cif
_cod_data_source_block           aghwla
_cod_depositor_comments
;Adding full bibliography for 1557262--1557263.cif.

 Adding full bibliography for 1557262--1557263.cif.
;
_cod_database_code               1557262
_nottingham_internal_coll_name   AGHWLA
_nottingham_internal_coll_number 17911
_nottingham_internal_coll_client AG/HWL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '1.00, 4.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczlt
_nottingham_internal_coll_date   10/09/2018
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'SN, XDA 017-09'
_nottingham_internal_process_date 11/09/2018
_nottingham_internal_process_user pczlt
_nottingham_internal_solution_date 15/07/2019
_nottingham_internal_solution_user pczlt
_nottingham_internal_refinement_date 15/07/2019
_nottingham_internal_refinement_user pczspa
_nottingham_internal_validation_date 15/07/2019
_nottingham_internal_validation_user pczspa
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C21 H21 F O2'
_chemical_oxdiff_usercomment
'AGHWA #17911 IN A FOMBLIN FILM ON A MICROMOUNT FOR AG/HWL'
_shelx_estimated_absorpt_t_max   0.855
_shelx_estimated_absorpt_t_min   0.711
_reflns_odcompleteness_completeness 99.93
_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
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O2-H2
 0.82 with sigma of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
3.b Aromatic/amide H refined with riding coordinates:
 C17(H17), C24(H24), C16(H16), C13(H13), C15(H15), C23(H23), C22(H22),
 C21(H21), C14(H14)
3.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C3(H3A,H3B,H3C)
;
_shelx_res_checksum              3880
_olex2_date_sample_submission    2018-09-06
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_original_sample_id AGHWLA
_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 1.331
_oxdiff_exptl_absorpt_empirical_full_min 0.829