Organocatalytic asymmetric electrophilic tandem selenylation semipinacol rearrangement of 1-(1-arylvinyl)cyclobutanols
Cao, Ren-Fei; Wei, Zheng-Wei; Li, Shu-Kun; Ding, Tong-Mei; Ke, Hua; Chen, Zhi-Min; Chemical Communications 61 (2025) 8532–8535; doi:10.1039/D5CC01919B

data_7134530
_publ_section_title
;
 Organocatalytic asymmetric electrophilic tandem selenylation semipinacol
 rearrangement of 1-(1-arylvinyl)cyclobutanols
;
_journal_issue                   47
_journal_name_full               'Chemical Communications'
_journal_page_first              8532
_journal_page_last               8535
_journal_paper_doi               10.1039/D5CC01919B
_journal_volume                  61
_journal_year                    2025
_chemical_absolute_configuration R
_chemical_formula_moiety         'C18 H18 F N O3 Se'
_chemical_formula_sum            'C18 H18 F N O3 Se'
_chemical_formula_weight         394.29
_chemical_name_common
(1S,2R)-2-(((4-fluoro-2-nitrophenyl)selanyl)methyl)-2-phenylcyclopentan-1-ol
_chemical_name_systematic
(1S,2R)-2-(((4-fluoro-2-nitrophenyl)selanyl)methyl)-2-phenylcyclopentan-1-ol
_chemical_properties_physical    Air-sensitive
_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
_audit_creation_date             2025-04-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2025-04-02 deposited with the CCDC.	2025-05-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.3528(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.23267(6)
_cell_length_b                   28.5347(2)
_cell_length_c                   8.41764(8)
_cell_measurement_reflns_used    27307
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      75.7710
_cell_measurement_theta_min      3.0630
_cell_volume                     1690.29(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.141a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.141a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.141a (Rigaku OD, 2024)'
_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_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.971
_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    -61.00 -31.00   0.50    0.05    -- -101.00  57.00 120.00   60
  2  \w    -63.00 -28.00   0.50    0.05    -- -101.00  57.00  30.00   70
  3  \w    -63.00 -28.00   0.50    0.05    -- -101.00  57.00 -30.00   70
  4  \w    -62.00 -29.00   0.50    0.05    -- -101.00  57.00-120.00   66
  5  \w    107.00 132.00   0.50    0.05    --  107.11 116.00 -56.00   50
  6  \w     36.00  82.00   0.50    0.05    --   47.70  37.00 -60.00   92
  7  \w     25.00  61.00   0.50    0.05    --   47.70  77.00 -60.00   72
  8  \w     87.00 112.00   0.50    0.05    --   47.70  37.00 -60.00   50
  9  \w     38.00  91.00   0.50    0.05    --   47.70  37.00  60.00  106
 10  \w     36.00  81.00   0.50    0.05    --   47.70  57.00  90.00   90
 11  \w     79.00 112.00   0.50    0.05    --  107.11 163.00  92.00   66
 12  \w     63.00  88.00   0.50    0.05    --   47.70 163.00  92.00   50
 13  \w     36.00  96.00   0.50    0.05    --   47.70  37.00-150.00  120
 14  \w    -97.00 -72.00   0.50    0.05    --  -47.70 163.00  92.00   50
 15  \w   -124.00 -98.00   0.50    0.05    -- -101.00 163.00  92.00   52
 16  \w   -101.00 -75.00   0.50    0.05    -- -101.00 116.00 -56.00   52
 17  \w    -75.00  -9.00   0.50    0.05    --  -47.70 116.00 -56.00  132
 18  \w     47.00 106.00   0.50    0.05    --  107.11 -99.00 -90.00  118
 19  \w     82.00 107.00   0.50    0.05    --  107.11-116.00-145.00   50
 20  \w     41.00  77.00   0.50    0.05    --  107.11-116.00-145.00   72
 21  \w     45.00  96.00   0.50    0.05    --  107.11 -99.00-120.00  102
 22  \w    106.00 137.00   0.50    0.05    --  107.11-163.00  65.00   62
 23  \w     42.00 109.00   0.50    0.05    --  107.11-125.00 150.00  134
 24  \w     53.00  94.00   0.50    0.05    --  107.11-125.00  60.00   82
 25  \w     37.00 106.00   0.50    0.05    --  107.11 -99.00  60.00  138
 26  \w     40.00  67.00   0.50    0.05    --  107.11 -57.00 120.00   54
 27  \w     59.00  84.00   0.50    0.05    --   47.70-163.00  65.00   50
 28  \w     91.00 116.00   0.50    0.05    --   47.70-163.00  65.00   50
 29  \w     13.00  88.00   0.50    0.05    --   47.70-116.00-145.00  150
 30  \w    -58.00 -25.00   0.50    0.05    --  -47.70 -77.00-150.00   66
 31  \w    -83.00 -25.00   0.50    0.05    --  -47.70 -77.00 -30.00  116
 32  \w    -84.00 -28.00   0.50    0.05    --  -47.70 -77.00 -60.00  112
 33  \w    -69.00 -25.00   0.50    0.05    --  -47.70 -77.00-180.00   88
 34  \w    -65.00 -25.00   0.50    0.05    --  -47.70 -77.00  30.00   80
 35  \w    -80.00 -33.00   0.50    0.05    --  -47.70 -57.00   0.00   94
 36  \w   -101.00 -76.00   0.50    0.05    --  -47.70 -77.00  90.00   50
 37  \w    -92.00 -26.00   0.50    0.05    --  -47.70 -77.00 120.00  132
 38  \w    -63.00 -25.00   0.50    0.05    --  -47.70 -77.00 150.00   76
 39  \w    -65.00 -25.00   0.50    0.05    --  -47.70 -77.00  90.00   80
 40  \w    -62.00 -33.00   0.50    0.05    --  -47.70 -57.00  60.00   58
 41  \w   -100.00 -68.00   0.50    0.05    --  -47.70 -57.00  60.00   64
 42  \w   -122.00 -43.00   0.50    0.05    --  -47.70 -19.00-180.00  158
 43  \w    -64.00 -33.00   0.50    0.05    --  -47.70 -57.00-120.00   62
 44  \w   -111.00 -78.00   0.50    0.05    -- -101.00 -77.00  -9.26   66
 45  \w   -105.00 -79.00   0.50    0.05    -- -101.00 -77.00 150.00   52
 46  \w   -163.00-137.00   0.50    0.05    -- -101.00 -77.00  -9.26   52
 47  \w   -173.00-114.00   0.50    0.05    -- -101.00 -77.00 -60.00  118
 48  \w   -104.00 -78.00   0.50    0.05    -- -101.00 -77.00 -90.00   52
 49  \w   -107.00 -79.00   0.50    0.05    -- -101.00 -77.00-150.00   56
 50  \w   -103.00 -78.00   0.50    0.05    -- -101.00 -77.00 -60.00   50
 51  \w   -114.00 -79.00   0.50    0.05    -- -101.00 -77.00 -30.00   70
 52  \w   -103.00 -78.00   0.50    0.05    -- -101.00 -77.00   0.00   50
 53  \w   -104.00 -78.00   0.50    0.05    -- -101.00 -77.00  30.00   52
 54  \w   -104.00 -79.00   0.50    0.05    -- -101.00 -74.00 122.71   50
 55  \w   -107.00 -82.00   0.50    0.05    -- -101.00 -72.00  96.84   50
 56  \w   -105.00 -78.00   0.50    0.05    -- -101.00 -76.00 162.40   54
 57  \w   -106.00 -80.00   0.50    0.05    -- -101.00 -72.00 171.00   52
 58  \w   -138.00-112.00   0.50    0.05    -- -101.00 -76.00 162.40   52
 59  \w   -172.00-113.00   0.50    0.05    -- -101.00 -72.00 171.00  118
 60  \w   -172.00-146.00   0.50    0.05    -- -101.00 -74.00 122.71   52
 61  \w   -173.00-118.00   0.50    0.05    -- -101.00 -67.00 145.64  110
 62  \w   -165.00 -82.00   0.50    0.05    -- -101.00 -67.00 -29.22  166
 63  \w   -150.00 -81.00   0.50    0.05    -- -101.00 -71.00-109.32  138
 64  \w   -107.00 -82.00   0.50    0.05    -- -101.00 -67.00-128.48   50
 65  \w   -106.00 -81.00   0.50    0.05    -- -101.00 -69.00-140.10   50
 66  \w   -107.00 -82.00   0.50    0.05    -- -101.00 -70.00-174.14   50
 67  \w   -119.00 -84.00   0.50    0.05    -- -101.00 -63.00  31.38   70
 68  \w   -166.00 -82.00   0.50    0.05    -- -101.00 -67.00  69.05  168
 69  \w   -154.00 -83.00   0.50    0.05    -- -101.00 -65.00  82.58  142
 70  \w   -112.00 -82.00   0.50    0.05    -- -101.00 -67.00 145.64   60
 71  \w   -109.00 -84.00   0.50    0.05    -- -101.00 -63.00 123.82   50
 72  \w   -165.00 -84.00   0.50    0.05    -- -101.00 -62.00  96.08  162
 73  \w   -167.00-144.50   0.50    0.05    -- -101.00 -62.00  46.63   45
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1781487000
_diffrn_orient_matrix_UB_12      -0.0102626000
_diffrn_orient_matrix_UB_13      -0.0651518000
_diffrn_orient_matrix_UB_21      -0.0152456000
_diffrn_orient_matrix_UB_22      -0.0523723000
_diffrn_orient_matrix_UB_23      0.0395826000
_diffrn_orient_matrix_UB_31      -0.1263098000
_diffrn_orient_matrix_UB_32      -0.0081638000
_diffrn_orient_matrix_UB_33      -0.1719649000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0234
_diffrn_reflns_av_unetI/netI     0.0148
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            34526
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.948
_diffrn_reflns_theta_min         3.097
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.245
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90855
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.141a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.549
_exptl_crystal_description       block
_exptl_crystal_F_000             800
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane/DCM'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.567
_refine_diff_density_min         -0.652
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 3025 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.028(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     415
_refine_ls_number_reflns         6810
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0345
_refine_ls_R_factor_gt           0.0327
_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^)+(0.0460P)^2^+0.8358P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0856
_refine_ls_wR_factor_ref         0.0867
_reflns_Friedel_coverage         0.923
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.934
_reflns_number_gt                6556
_reflns_number_total             6810
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc01919b2.cif
_cod_data_source_block           chenzmwzw-ii-167b_auto
_cod_depositor_comments
'Adding full bibliography for 7134529--7134530.cif.'
_cod_database_code               7134530
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHONSe
_shelx_estimated_absorpt_t_max   0.855
_shelx_estimated_absorpt_t_min   0.697
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H) groups
2. Restrained distances
 H3-O3
 0.88 with sigma of 0.02
 H6A-O6
 0.88 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(F2) = Uanis(F1)
Uanis(C16) = Uanis(C17)
Uanis(C15) = Uanis(C14)
Uanis(F2) = Uanis(C22)
4.a Ternary CH refined with riding coordinates:
 C12(H12), C30(H30)
4.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C25(H25A,H25B),
 C27(H27A,H27B), C28(H28A,H28B), C29(H29A,H29B)
4.c Aromatic/amide H refined with riding coordinates:
 C3(H3A), C5(H5), C6(H6), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18),
 C21(H21), C23(H23), C24(H24), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36)
;
_shelx_res_checksum              55169
_shelx_hkl_checksum              4585
_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 1.205
_oxdiff_exptl_absorpt_empirical_full_min 0.867