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_4131999
_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 syn
_chemical_formula_moiety         'C32 H38 O2'
_chemical_formula_sum            'C32 H38 O2'
_chemical_formula_weight         454.62
_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                 91.3423(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.24067(7)
_cell_length_b                   7.76255(4)
_cell_length_c                   24.83830(13)
_cell_measurement_reflns_used    53419
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      78.2630
_cell_measurement_theta_min      1.7910
_cell_volume                     2552.21(2)
_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    -39.00  81.00   0.50    0.25    --    0.00  57.00 -30.00  240
  2  \w     95.00 151.00   0.50    5.00    --   62.87 119.00 -53.00  112
  3  \w     96.00 178.00   0.50    5.00    --  125.75 119.00 -53.00  164
  4  \w    100.00 178.00   0.50    5.00    --  125.75 111.00 -90.00  156
  5  \w     91.00 150.00   0.50    5.00    --   62.87 125.00-120.00  118
  6  \w     91.00 150.00   0.50    5.00    --   62.87 125.00 -90.00  118
  7  \w     87.00 178.00   0.50    5.00    --  125.75  63.00 -90.00  182
  8  \w     87.00 178.00   0.50    5.00    --  125.75  63.00  60.00  182
  9  \w     87.00 178.00   0.50    5.00    --  125.75  63.00 120.00  182
 10  \w     87.00 178.00   0.50    5.00    --  125.75  63.00  30.00  182
 11  \w     87.00 178.00   0.50    5.00    --  125.75  63.00 150.00  182
 12  \w     86.00 178.00   0.50    5.00    --  125.75  65.00 -26.72  184
 13  \w     87.00 178.00   0.50    5.00    --  125.75  63.00-180.00  182
 14  \w     87.00 178.00   0.50    5.00    --  125.75  63.00 -60.00  182
 15  \w     87.00 178.00   0.50    5.00    --  125.75  63.00  90.00  182
 16  \w     72.00 150.00   0.50    5.00    --   62.87 156.00 102.00  156
 17  \w     80.00 178.00   0.50    5.00    --  125.75  77.00  60.00  196
 18  \w     71.00 166.00   0.50    5.00    --  125.75 156.00 102.00  190
 19  \w     80.00 178.00   0.50    5.00    --  125.75  77.00  90.00  196
 20  \w     82.00 178.00   0.50    5.00    --  125.75  50.00 150.00  192
 21  \w     80.00 178.00   0.50    5.00    --  125.75  77.00 -60.00  196
 22  \w     78.00 178.00   0.50    5.00    --  125.75  82.00 -18.19  200
 23  \w     80.00 178.00   0.50    5.00    --  125.75  77.00  30.00  196
 24  \w     80.00 178.00   0.50    5.00    --  125.75  77.00-150.00  196
 25  \w     82.00 178.00   0.50    5.00    --  125.75  72.00-151.19  192
 26  \w     80.00 178.00   0.50    5.00    --  125.75  77.00 -90.00  196
 27  \w     80.00 178.00   0.50    5.00    --  125.75  77.00-120.00  196
 28  \w     80.00 178.00   0.50    5.00    --  125.75  77.00   0.00  196
 29  \w     80.00 178.00   0.50    5.00    --  125.75  77.00 -30.00  196
 30  \w     80.00 178.00   0.50    5.00    --  125.75  77.00 150.00  196
 31  \w     60.00 149.00   0.50    5.00    --  125.75 178.00 150.00  178
 32  \w     13.00  46.00   0.50    5.00    --   62.87  85.00 -20.72   66
 33  \w     10.00  44.00   0.50    5.00    --   62.87  92.00 -93.62   68
 34  \w     17.00 151.00   0.50    5.00    --   62.87  77.00-180.00  268
 35  \w     80.00 178.00   0.50    5.00    --  125.75  77.00-180.00  196
 36  \w     60.00 149.00   0.50    5.00    --  125.75 178.00-180.00  178
 37  \w     12.00  46.00   0.50    5.00    --   62.87  89.00  36.44   68
 38  \w      9.00  37.00   0.50    5.00    --   62.87  94.00  95.77   56
 39  \w     10.00  37.00   0.50    5.00    --   62.87  93.00 146.05   54
 40  \w     10.00  44.00   0.50    5.00    --   62.87  92.00  83.36   68
 41  \w      9.00  37.00   0.50    5.00    --   62.87  94.00  51.39   56
 42  \w     13.00  46.00   0.50    5.00    --   62.87  85.00  14.07   66
 43  \w     10.00  37.00   0.50    5.00    --   62.87  93.00 -52.88   54
 44  \w     10.00  37.00   0.50    5.00    --   62.87  93.00-111.55   54
 45  \w     10.00  44.00   0.50    5.00    --   62.87  92.00-165.70   68
 46  \w      9.00  37.00   0.50    5.00    --   62.87  94.00-178.79   56
 47  \w    -39.00  81.00   0.50    0.25    --    0.00  57.00 -30.00  240
 48  \w     -4.00  57.00   0.50    0.25    --    0.00 -99.00 150.00  122
 49  \w     47.00 137.00   0.50    5.00    --   62.87-156.00  65.00  180
 50  \w     47.00 137.00   0.50    5.00    --  125.75-156.00  65.00  180
 51  \w     43.00 165.00   0.50    5.00    --  125.75 -63.00  30.00  244
 52  \w     38.00 117.00   0.50    5.00    --  125.75-119.00-138.00  158
 53  \w     43.00 165.00   0.50    5.00    --  125.75 -63.00-180.00  244
 54  \w     36.00 115.00   0.50    5.00    --  125.75-111.00 -60.00  158
 55  \w     34.00 172.00   0.50    5.00    --  125.75 -77.00-120.00  276
 56  \w     27.00 117.00   0.50    5.00    --   62.87-119.00-138.00  180
 57  \w     36.00 115.00   0.50    5.00    --  125.75-111.00   0.00  158
 58  \w     36.00 115.00   0.50    5.00    --  125.75-111.00 150.00  158
 59  \w    -46.00  89.00   0.50    0.25    --    0.00  77.00  90.00  270
 60  \w    -67.00  -6.00   0.50    0.25    --    0.00 119.00 -53.00  122
 61  \w    -89.00 -27.00   0.50    0.25    --    0.00 156.00 102.00  124
 62  \w    -89.00 -16.00   0.50    5.00    -- -104.25 111.00  90.00  146
 63  \w   -111.00 -26.00   0.50    5.00    --  -62.87 156.00 102.00  170
 64  \w   -112.00 -26.00   0.50    5.00    -- -104.25 156.00 102.00  172
 65  \w    -99.00  89.00   0.50    0.25    --    0.00   0.00 -90.00  376
 66  \w    -81.00  38.00   0.50    0.25    --    0.00 -57.00 120.00  238
 67  \w    -99.00  89.00   0.50    0.25    --    0.00   0.00-150.00  376
 68  \w    -98.00 -36.00   0.50    0.25    --    0.00 178.00-180.00  124
 69  \w   -101.00  19.00   0.50    5.00    --  -62.87  61.00-180.00  240
 70  \w    -99.00  89.00   0.50    0.25    --    0.00   0.00 -60.00  376
 71  \w    -99.00  89.00   0.50    0.25    --    0.00   0.00-180.00  376
 72  \w    -99.00  89.00   0.50    0.25    --    0.00   0.00-120.00  376
 73  \w   -145.00 -25.00   0.50    5.00    --  -62.87 -61.00-120.00  240
 74  \w   -145.00 -25.00   0.50    5.00    --  -62.87 -61.00 -90.00  240
 75  \w   -145.00 -25.00   0.50    5.00    --  -62.87 -61.00  60.00  240
 76  \w   -145.00 -25.00   0.50    5.00    --  -62.87 -61.00  90.00  240
 77  \w   -150.00 -49.00   0.50    5.00    --  -62.87-156.00  65.00  202
 78  \w   -150.00 -74.00   0.50    5.00    --  -62.87-119.00-138.00  152
 79  \w   -148.00 -14.00   0.50    5.00    --  -62.87 -45.00 -60.00  268
 80  \w   -148.00 -14.00   0.50    5.00    --  -62.87 -45.00  30.00  268
 81  \w   -149.00 -49.00   0.50    5.00    -- -104.25-156.00  65.00  200
 82  \w   -156.00 -80.00   0.50    5.00    --  -62.87 -94.00 150.00  152
 83  \w   -156.00 -80.00   0.50    5.00    --  -62.87 -94.00 120.00  152
 84  \w   -154.00 -17.00   0.50    5.00    --  -62.87 -77.00   0.00  274
 85  \w   -154.00 -17.00   0.50    5.00    --  -62.87 -77.00-180.00  274
 86  \w   -156.00 -80.00   0.50    5.00    --  -62.87 -94.00-150.00  152
 87  \w   -154.00 -17.00   0.50    5.00    --  -62.87 -77.00 -90.00  274
 88  \w   -177.00 -74.00   0.50    5.00    -- -104.25-119.00-138.00  206
 89  \w   -177.00 -56.00   0.50    5.00    -- -104.25 -80.00 -78.36  242
 90  \w   -177.00 -55.00   0.50    5.00    -- -104.25 -83.00 132.09  244
 91  \w   -177.00 -56.00   0.50    5.00    -- -104.25 -80.00 -52.05  242
 92  \w   -177.00 -56.00   0.50    5.00    -- -104.25 -80.00  74.56  242
 93  \w   -177.00 -58.00   0.50    5.00    -- -104.25 -77.00  81.26  238
 94  \w   -177.00 -56.00   0.50    5.00    -- -104.25 -81.00 -30.13  242
 95  \w   -177.00 -58.00   0.50    5.00    -- -104.25 -77.00-120.00  238
 96  \w   -177.00 -58.00   0.50    5.00    -- -104.25 -77.00  60.00  238
 97  \w   -177.00 -56.00   0.50    5.00    -- -104.25 -81.00  43.90  242
 98  \w   -177.00 -56.00   0.50    5.00    -- -104.25 -81.00-132.91  242
 99  \w   -177.00 -58.00   0.50    5.00    -- -104.25 -77.00 -90.00  238
100  \w   -177.00 -56.00   0.50    5.00    -- -104.25 -81.00 116.64  242
101  \w   -177.00 -55.00   0.50    5.00    -- -104.25 -83.00  24.60  244
102  \w   -177.00 -59.00   0.50    5.00    -- -104.25 -76.00  94.62  236
103  \w   -177.00 -58.00   0.50    5.00    -- -104.25 -78.00 164.77  238
104  \w   -177.00 -56.00   0.50    5.00    -- -104.25 -81.00 152.50  242
105  \w   -177.00 -58.00   0.50    5.00    -- -104.25 -77.00   0.00  238
106  \w   -177.00 -58.00   0.50    5.00    -- -104.25 -77.00-150.00  238
107  \w   -177.00 -59.00   0.50    5.00    -- -104.25 -75.00-176.87  236
108  \w   -177.00 -55.00   0.50    5.00    -- -104.25 -83.00  -6.27  244
109  \w   -177.00 -55.00   0.50    5.00    -- -104.25 -83.00-100.29  244
110  \w   -177.00 -58.00   0.50    5.00    -- -104.25 -77.00 173.31  238
;
_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      -0.0944643000
_diffrn_orient_matrix_UB_12      -0.1129283000
_diffrn_orient_matrix_UB_13      0.0070304000
_diffrn_orient_matrix_UB_21      0.0215413000
_diffrn_orient_matrix_UB_22      -0.0070380000
_diffrn_orient_matrix_UB_23      0.0611918000
_diffrn_orient_matrix_UB_31      -0.0644415000
_diffrn_orient_matrix_UB_32      0.1630506000
_diffrn_orient_matrix_UB_33      0.0075107000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0338
_diffrn_reflns_av_unetI/netI     0.0127
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            94575
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.065
_diffrn_reflns_theta_min         1.779
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.550
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.851
_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    1.183
_exptl_crystal_description       plate
_exptl_crystal_F_000             984
_exptl_crystal_size_max          0.168
_exptl_crystal_size_mid          0.099
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.263
_refine_diff_density_min         -0.181
_refine_diff_density_rms         0.030
_refine_ls_abs_structure_details
;
 Flack x determined using 4326 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     619
_refine_ls_number_reflns         9697
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0318
_refine_ls_R_factor_gt           0.0315
_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^)+(0.0453P)^2^+0.5968P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0822
_refine_ls_wR_factor_ref         0.0824
_reflns_Friedel_coverage         0.851
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                9584
_reflns_number_total             9697
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b13710_si_003.cif
_cod_data_source_block           rwh11_abs
_cod_database_code               4131999
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C32H38O2
_chemical_oxdiff_usercomment     'Crystallized from diethyl ether.'
_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:
 C108(H108), C112(H112), C118(H118), C119(H119), C126(H126), C208(H208),
 C212(H212), C218(H218), C219(H219), C226(H226)
2.b Secondary CH2 refined with riding coordinates:
 C109(H10A,H10B), C111(H11A,H11B), C116(H11C,H11D), C117(H11E,H11F), C120(H12A,
 H12B), C121(H12C,H12D), C124(H12E,H12F), C125(H12G,H12H), C209(H20A,H20B),
 C211(H21A,H21B), C216(H21C,H21D), C217(H21E,H21F), C220(H22A,H22B), C221(H22C,
 H22D), C224(H22E,H22F), C225(H22G,H22H)
2.c Aromatic/amide H refined with riding coordinates:
 C101(H101), C102(H102), C103(H103), C104(H104), C105(H105), C114(H114),
 C128(H128), C129(H129), C201(H201), C202(H202), C203(H203), C204(H204),
 C205(H205), C214(H214), C228(H228), C229(H229)
2.d Idealised Me refined as rotating group:
 C130(H13A,H13B,H13C), C131(H13D,H13E,H13F), C132(H13G,H13H,H13I), C230(H23A,
 H23B,H23C), C231(H23D,H23E,H23F), C232(H23G,H23H,H23I)
;
_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 1.392
_oxdiff_exptl_absorpt_empirical_full_min 0.795