Chiral Lewis acid-catalyzed enantioselective cyclopropanation and C-H insertion reactions of vinyl ketones with α-diazoesters.
Zhao, Peng; Wu, Simeng; Ke, Chaoqi; Liu, Xiaohua; Feng, Xiaoming; Chemical communications (Cambridge, England) 54 (2018) 9837–9840; doi:10.1039/c8cc05420g

data_7122187
_publ_section_title
;
 Chiral Lewis acid-catalyzed enantioselective cyclopropanation and C-H
 insertion reactions of vinyl ketones with \a-diazoesters.
;
_journal_issue                   70
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              9837
_journal_page_last               9840
_journal_paper_doi               10.1039/c8cc05420g
_journal_volume                  54
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         '6(C25 H22 O3)'
_chemical_formula_sum            'C150 H132 O18'
_chemical_formula_weight         2222.55
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-06-29
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2018-05-17 deposited with the CCDC.
2018-08-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.5840(14)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.42491(19)
_cell_length_b                   18.47453(19)
_cell_length_c                   20.7026(3)
_cell_measurement_reflns_used    13889
_cell_measurement_temperature    150
_cell_measurement_theta_max      72.5750
_cell_measurement_theta_min      4.1380
_cell_volume                     5954.49(14)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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      air
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_details
;
  1 omega  -31.00   63.00   1.0000    1.6200
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -77.0000 -120.0000 94

  2 omega   10.00  104.00   1.0000    1.6200
omega____ theta____ kappa____ phi______ frames
    -       36.4171   77.0000  -90.0000 94

  3 omega    1.00   75.00   1.0000    1.6200
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -99.0000  -60.0000 74

  4 omega  -31.00   53.00   1.0000    1.6200
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -57.0000  -90.0000 84

  5 omega   20.00  104.00   1.0000    1.6200
omega____ theta____ kappa____ phi______ frames
    -       36.4171   57.0000  150.0000 84

  6 omega   20.00  104.00   1.0000    1.6200
omega____ theta____ kappa____ phi______ frames
    -       36.4171   57.0000   60.0000 84

  7 omega    1.00   75.00   1.0000    1.6200
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -99.0000    0.0000 74

  8 omega   20.00  104.00   1.0000    1.6200
omega____ theta____ kappa____ phi______ frames
    -       36.4171   57.0000   30.0000 84

  9 omega  -33.00   55.00   1.0000    1.6200
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -38.0000  150.0000 88

 10 omega   57.00  150.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  178.0000   30.0000 93

 11 omega   39.00  106.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -150.0000 67

 12 omega   49.00   76.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -90.0000 27

 13 omega   47.00   97.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  120.0000 50

 14 omega   38.00   72.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -30.0000 34

 15 omega   38.00   91.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000    0.0000 53

 16 omega   43.00   70.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -60.0000 27

 17 omega   93.00  175.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000  150.0000 82

 18 omega   57.00   91.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   30.0000 34

 19 omega   41.00  135.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000   30.0000 94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0846311000
_diffrn_orient_matrix_UB_12      0.0153371000
_diffrn_orient_matrix_UB_13      -0.0146804000
_diffrn_orient_matrix_UB_21      0.0459818000
_diffrn_orient_matrix_UB_22      0.0118789000
_diffrn_orient_matrix_UB_23      0.0766651000
_diffrn_orient_matrix_UB_31      0.0226655000
_diffrn_orient_matrix_UB_32      -0.0810933000
_diffrn_orient_matrix_UB_33      0.0084528000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0336
_diffrn_reflns_av_unetI/netI     0.0394
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            34181
_diffrn_reflns_point_group_measured_fraction_full 0.736
_diffrn_reflns_point_group_measured_fraction_max 0.710
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.624
_diffrn_reflns_theta_min         4.507
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.640
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67158
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.240
_exptl_crystal_description       block
_exptl_crystal_F_000             2352
_exptl_crystal_size_max          0.55
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.4
_refine_diff_density_max         0.592
_refine_diff_density_min         -0.300
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 3506 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1519
_refine_ls_number_reflns         16801
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0629
_refine_ls_R_factor_gt           0.0524
_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^)+(0.0958P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1333
_refine_ls_wR_factor_ref         0.1437
_reflns_Friedel_coverage         0.408
_reflns_Friedel_fraction_full    0.455
_reflns_Friedel_fraction_max     0.426
_reflns_number_gt                13826
_reflns_number_total             16801
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc05420g2.cif
_cod_data_source_block           fxm-wsm-157u-150k
_cod_depositor_comments
'Adding full bibliography for 7122187--7122188.cif.'
_cod_original_cell_volume        5954.50(14)
_cod_database_code               7122187
_reflns_odcompleteness_completeness 99.87
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C01A(H01A,H01B), C01J(H01C,H01D), C020(H02A,H02B), C023(H02Q,H02S), C029(H02,
 H), C02E(H02F,H02G), C02T(H02C,H02D), C02X(H1AA,HA), C037(H03M,H03O),
 C038(H03F,H03G), C03F(H03I,H03J), C03I(H03B,H03C)
2.b Aromatic/amide H refined with riding coordinates:
 C00U(H00U), C00X(H00X), C011(H011), C015(H015), C018(H018), C01E(H01E),
 C01F(H01F), C01G(H01G), C01K(H01K), C01P(H01P), C01Q(H01Q), C01T(H01T),
 C01U(H01U), C01V(H01V), C01W(H01W), C01X(H01X), C01Y(H01Y), C024(H024),
 C025(H025), C028(H028), C02A(H02K), C02C(H02E), C02D(H02T), C02F(H02H),
 C02G(H02I), C02H(H02M), C02J(H02J), C02K(H02N), C02L(H02L), C02N(H02O),
 C02O(H02X), C02P(H02P), C02Q(H0AA), C02R(H02R), C02S(H02Y), C02U(H02U),
 C02V(H02V), C02W(H02W), C02Y(H02Z), C02Z(H2AA), C030(H030), C031(H031),
 C032(H032), C033(H033), C034(H034), C035(H035), C036(H036), C039(H039),
 C03A(H03A), C03B(H3AA), C03C(H03H), C03D(H03D), C03E(H03E), C03G(H4AA),
 C03H(H5AA), C03J(H03R), C03K(H03K), C03L(H03L), C03N(H03N), C03O(H6AA),
 C03P(H03P), C03Q(H03Q), C03R(H03S), C03S(H03T), C03T(H03U), C03U(H03),
 C03V(H03V), C03W(H03W), C03X(H03X), C03Y(H03Y), C03Z(H03Z), C040(H040),
 C041(H041), C042(H042), C043(H043), C044(H044), C045(H045), C046(H046),
 C047(H047), C048(H048), C04A(H04A), C04B(H04W), C04C(H04K), C04D(H04L),
 C04F(H04M), C04G(H04X), C04J(H04U), C04K(H04Y), C04L(H04Q), C04O(H04V)
2.c Idealised Me refined as rotating group:
 C049(H04H,H04I,H04J), C04E(H04E,H04F,H04G), C04H(H04N,H04O,H04P), C04I(H04R,
 H04S,H04T), C04M(H04Z,HB,HC), C04N(H04B,H04C,H04D)
;
_shelx_res_checksum              24182
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2017-06-28
_olex2_submission_special_instructions 'No special instructions were received'