Diastereo- and Enantioselective Formal [3 + 2] Cycloaddition of Cyclopropyl Ketones and Alkenes via Ti-Catalyzed Radical Redox Relay.
Hao, Wei; Harenberg, Johannes H.; Wu, Xiangyu; MacMillan, Samantha N.; Lin, Song; Journal of the American Chemical Society 140 (2018) 3514–3517; doi:10.1021/jacs.7b13710

data_4132000
_publ_section_title
;
 Diastereo- and Enantioselective Formal [3 + 2] Cycloaddition of
 Cyclopropyl Ketones and Alkenes via Ti-Catalyzed Radical Redox Relay.
;
_journal_issue                   10
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3514
_journal_page_last               3517
_journal_paper_doi               10.1021/jacs.7b13710
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H22 O'
_chemical_formula_sum            'C20 H22 O'
_chemical_formula_weight         278.37
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-14
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2016.08.26 svn.r3337 for Rigaku Oxford Diffraction, GUI svn.r5221)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.485(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.84080(10)
_cell_length_b                   16.7324(4)
_cell_length_c                   7.8935(2)
_cell_measurement_reflns_used    24721
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      78.4910
_cell_measurement_theta_min      5.2650
_cell_volume                     770.71(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_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    -46.00  85.00   0.50    0.48    --    0.00  48.00 -27.00  262
  2  \w     17.00 148.00   0.50    2.73    --   62.87  48.00 -27.00  262
  3  \w     91.00 150.00   0.50    2.73    --   62.87 125.00  60.00  118
  4  \w     80.00 178.00   0.50    5.51    --  125.75  48.00 -27.00  196
  5  \w    100.00 178.00   0.50    5.51    --  125.75 111.00-180.00  156
  6  \w     91.00 150.00   0.50    2.73    --   62.87 125.00-180.00  118
  7  \w     91.00 150.00   0.50    2.73    --   62.87 125.00 -90.00  118
  8  \w     87.00 178.00   0.50    5.51    --  125.75  63.00-150.00  182
  9  \w     87.00 178.00   0.50    5.51    --  125.75  63.00   0.00  182
 10  \w     87.00 178.00   0.50    5.51    --  125.75  63.00 150.00  182
 11  \w     87.00 178.00   0.50    5.51    --  125.75  63.00 120.00  182
 12  \w     87.00 178.00   0.50    5.51    --  125.75  63.00  60.00  182
 13  \w     87.00 178.00   0.50    5.51    --  125.75  63.00 -90.00  182
 14  \w     87.00 178.00   0.50    5.51    --  125.75  63.00-180.00  182
 15  \w     80.00 178.00   0.50    5.51    --  125.75  77.00 -60.00  196
 16  \w     87.00 178.00   0.50    5.51    --  125.75  63.00  30.00  182
 17  \w     80.00 178.00   0.50    5.51    --  125.75  77.00  90.00  196
 18  \w     80.00 178.00   0.50    5.51    --  125.75  77.00 150.00  196
 19  \w     82.00 178.00   0.50    5.51    --  125.75  50.00  90.00  192
 20  \w     80.00 178.00   0.50    5.51    --  125.75  77.00  30.00  196
 21  \w     80.00 178.00   0.50    5.51    --  125.75  77.00-150.00  196
 22  \w     82.00 178.00   0.50    5.51    --  125.75  50.00  60.00  192
 23  \w     80.00 178.00   0.50    5.51    --  125.75  77.00 120.00  196
 24  \w     80.00 178.00   0.50    5.51    --  125.75  77.00 -30.00  196
 25  \w     80.00 178.00   0.50    5.51    --  125.75  77.00 -90.00  196
 26  \w     81.00 178.00   0.50    5.51    --  125.75  75.00-125.64  194
 27  \w     80.00 178.00   0.50    5.51    --  125.75  77.00  60.00  196
 28  \w     82.00 178.00   0.50    5.51    --  125.75  50.00 -90.00  192
 29  \w     80.00 178.00   0.50    5.51    --  125.75  77.00-180.00  196
 30  \w     80.00 178.00   0.50    5.51    --  125.75  77.00   0.00  196
 31  \w     80.00 178.00   0.50    5.51    --  125.75  77.00-120.00  196
 32  \w     81.00 178.00   0.50    5.51    --  125.75  76.00 -71.74  194
 33  \w     60.00 149.00   0.50    5.51    --  125.75 178.00 -90.00  178
 34  \w     60.00 149.00   0.50    5.51    --  125.75 178.00-150.00  178
 35  \w     62.00 178.00   0.50    5.51    --  125.75  37.00  30.00  232
 36  \w     60.00 149.00   0.50    5.51    --  125.75 178.00  90.00  178
 37  \w     17.00 151.00   0.50    2.73    --   62.87  77.00-120.00  268
 38  \w     43.00 165.00   0.50    5.51    --  125.75 -63.00 -60.00  244
 39  \w     41.00 172.00   0.50    5.51    --  125.75 -48.00-174.00  262
 40  \w     43.00 165.00   0.50    5.51    --  125.75 -63.00   0.00  244
 41  \w     31.00 121.00   0.50    2.73    --   62.87-125.00 -90.00  180
 42  \w     36.00 115.00   0.50    5.51    --  125.75-111.00  60.00  158
 43  \w     32.00 178.00   0.50    5.51    --  125.75 -91.00 -30.00  292
 44  \w     34.00 172.00   0.50    5.51    --  125.75 -77.00-180.00  276
 45  \w     25.00 145.00   0.50    2.73    --   62.87  61.00  90.00  240
 46  \w     43.00 165.00   0.50    5.51    --  125.75 -63.00 150.00  244
 47  \w     36.00 115.00   0.50    5.51    --  125.75-111.00  90.00  158
 48  \w     32.00 178.00   0.50    5.51    --  125.75 -91.00  30.00  292
 49  \w     36.00 115.00   0.50    5.51    --  125.75-111.00-120.00  158
 50  \w     36.00 115.00   0.50    5.51    --  125.75-111.00-150.00  158
 51  \w     36.00 115.00   0.50    5.51    --  125.75-111.00 -90.00  158
 52  \w     36.00 115.00   0.50    5.51    --  125.75-111.00-180.00  158
 53  \w     32.00 178.00   0.50    5.51    --  125.75 -91.00 -90.00  292
 54  \w     42.00 171.00   0.50    5.51    --  125.75 -50.00 120.00  258
 55  \w     27.00 178.00   0.50    5.51    --  125.75   0.00-120.00  302
 56  \w     28.00 178.00   0.50    5.51    --  125.75  12.00-180.00  300
 57  \w      9.00  37.00   0.50    2.73    --   62.87  94.00   0.26   56
 58  \w     11.00  46.00   0.50    2.73    --   62.87  90.00  61.00   70
 59  \w     17.00 151.00   0.50    2.73    --   62.87  77.00 150.00  268
 60  \w     12.00  46.00   0.50    2.73    --   62.87  89.00  41.63   68
 61  \w     12.00  46.00   0.50    2.73    --   62.87  88.00  17.64   68
 62  \w     10.00  44.00   0.50    2.73    --   62.87  92.00 -70.13   68
 63  \w     10.00  37.00   0.50    2.73    --   62.87  93.00-141.91   54
 64  \w     17.00 151.00   0.50    2.73    --   62.87  77.00-180.00  268
 65  \w     17.00 151.00   0.50    2.73    --   62.87  77.00-180.00  268
 66  \w     10.00  37.00   0.50    2.73    --   62.87  93.00  55.23   54
 67  \w    -46.00  89.00   0.50    0.48    --    0.00  77.00 120.00  270
 68  \w     -4.00  57.00   0.50    0.48    --    0.00 -99.00 -90.00  122
 69  \w     -4.00  57.00   0.50    0.48    --    0.00 -99.00-180.00  122
 70  \w    -22.00 109.00   0.50    2.73    --   62.87 -48.00-174.00  262
 71  \w    -16.00 108.00   0.50    2.73    --   62.87 -94.00  90.00  248
 72  \w    -39.00  81.00   0.50    0.48    --    0.00  57.00-150.00  240
 73  \w    -36.00 151.00   0.50    2.73    --   62.87   0.00 -30.00  374
 74  \w    -36.00 151.00   0.50    2.73    --   62.87   0.00 -90.00  374
 75  \w    -36.00 151.00   0.50    2.73    --   62.87   0.00-120.00  374
 76  \w    -36.00 151.00   0.50    2.73    --   62.87   0.00 -60.00  374
 77  \w    -36.00 151.00   0.50    2.73    --   62.87   0.00-150.00  374
 78  \w    -36.00 151.00   0.50    2.73    --   62.87   0.00   0.00  374
 79  \w    -36.00 151.00   0.50    2.73    --   62.87   0.00  90.00  374
 80  \w    -36.00 151.00   0.50    2.73    --   62.87   0.00-180.00  374
 81  \w    -36.00 151.00   0.50    2.73    --   62.87   0.00  60.00  374
 82  \w    -36.00 151.00   0.50    2.73    --   62.87   0.00  30.00  374
 83  \w    -85.00  46.00   0.50    0.48    --    0.00 -48.00-174.00  262
 84  \w    -98.00 -36.00   0.50    0.48    --    0.00 178.00  30.00  124
 85  \w    -94.00 -10.00   0.50    2.73    --  -62.87 125.00-120.00  168
 86  \w    -99.00  89.00   0.50    0.48    --    0.00   0.00-120.00  376
 87  \w   -109.00  22.00   0.50    2.73    --  -62.87  48.00 -27.00  262
 88  \w    -99.00  89.00   0.50    0.48    --    0.00   0.00-180.00  376
 89  \w    -99.00  89.00   0.50    0.48    --    0.00   0.00-150.00  376
 90  \w   -147.00 -17.00   0.50    2.73    --  -62.87 -48.00-174.00  260
 91  \w   -150.00 -19.00   0.50    5.51    -- -104.25  48.00 -27.00  262
 92  \w   -148.00 -14.00   0.50    2.73    --  -62.87 -45.00  30.00  268
 93  \w   -148.00 -14.00   0.50    2.73    --  -62.87 -45.00  60.00  268
 94  \w   -145.00 -25.00   0.50    2.73    --  -62.87 -61.00-150.00  240
 95  \w   -177.00 -58.00   0.50    5.51    -- -104.25 -48.00-174.00  238
 96  \w   -177.00 -58.00   0.50    5.51    -- -104.25 -77.00  30.00  238
 97  \w   -177.00 -65.00   0.50    5.51    -- -104.25 -63.00  30.00  224
 98  \w   -177.00 -59.00   0.50    5.51    -- -104.25 -75.00 106.47  236
 99  \w   -177.00 -58.00   0.50    5.51    -- -104.25 -77.00 150.00  238
100  \w   -177.00 -58.00   0.50    5.51    -- -104.25 -78.00  88.88  238
101  \w   -177.00 -59.00   0.50    5.51    -- -104.25 -76.00  74.71  236
102  \w   -177.00 -58.00   0.50    5.51    -- -104.25 -77.00 120.00  238
103  \w   -177.00 -56.00   0.50    5.51    -- -104.25 -81.00 143.88  242
104  \w   -177.00 -58.00   0.50    5.51    -- -104.25 -77.00   0.00  238
105  \w   -177.00 -58.00   0.50    5.51    -- -104.25 -77.00-180.00  238
106  \w   -177.00 -58.00   0.50    5.51    -- -104.25 -77.00  60.00  238
107  \w   -177.00 -55.00   0.50    5.51    -- -104.25 -83.00-120.53  244
108  \w   -177.00 -58.00   0.50    5.51    -- -104.25 -77.00-120.00  238
109  \w   -177.00 -59.00   0.50    5.51    -- -104.25 -75.00 -13.70  236
110  \w   -177.00 -56.00   0.50    5.51    -- -104.25 -82.00 175.47  242
111  \w   -177.00 -58.00   0.50    5.51    -- -104.25 -77.00 -41.98  238
112  \w   -177.00 -59.00   0.50    5.51    -- -104.25 -75.00 -77.90  236
113  \w   -177.00 -56.00   0.50    5.51    -- -104.25 -82.00 -89.77  242
114  \w   -177.00 -56.00   0.50    5.51    -- -104.25 -82.00-152.49  242
115  \w   -177.00 -61.00   0.50    5.51    -- -104.25 -72.00 -32.06  232
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0018721000
_diffrn_orient_matrix_UB_12      0.0101260000
_diffrn_orient_matrix_UB_13      0.1939524000
_diffrn_orient_matrix_UB_21      0.2127202000
_diffrn_orient_matrix_UB_22      0.0542574000
_diffrn_orient_matrix_UB_23      -0.0047982000
_diffrn_orient_matrix_UB_31      -0.1563081000
_diffrn_orient_matrix_UB_32      0.0736839000
_diffrn_orient_matrix_UB_33      -0.0231083000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0252
_diffrn_reflns_av_unetI/netI     0.0083
_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       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            31128
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.012
_diffrn_reflns_theta_min         5.287
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.549
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.563
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.29d (Rigaku Oxford Diffraction, 2017)
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_density_diffrn    1.200
_exptl_crystal_description       block
_exptl_crystal_F_000             300
_exptl_crystal_size_max          0.236
_exptl_crystal_size_mid          0.179
_exptl_crystal_size_min          0.127
_refine_diff_density_max         0.161
_refine_diff_density_min         -0.168
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 1391 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.04(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     192
_refine_ls_number_reflns         2923
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0266
_refine_ls_R_factor_gt           0.0265
_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^)+(0.0438P)^2^+0.1271P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0706
_refine_ls_wR_factor_ref         0.0715
_reflns_Friedel_coverage         0.924
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                2921
_reflns_number_total             2923
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b13710_si_002.cif
_cod_data_source_block           rwh10_abs
_cod_database_code               4132000
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C20H22O
_chemical_oxdiff_usercomment     'Crystallized from Et2O.'
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_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 Ternary CH refined with riding coordinates:
 C8(H8), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C14(H14), C15(H15), C16(H16),
 C17(H17), C18(H18)
2.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
;
_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 4.504
_oxdiff_exptl_absorpt_empirical_full_min 0.687