Directed Cu(I)-Catalyzed Carbomagnesiation of 1-Arylcycloprop-2-ene-1-carboxamides En Route to Densely Substituted Functionalized Cyclopropanes.
Edwards, Andrew; Rubin, Michael; The Journal of organic chemistry 83 (2018) 8426–8448; doi:10.1021/acs.joc.8b01063

data_4035577
_publ_section_title
;
 Directed Cu(I)-Catalyzed Carbomagnesiation of
 1-Arylcycloprop-2-ene-1-carboxamides En Route to Densely Substituted
 Functionalized Cyclopropanes.
;
_journal_issue                   15
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              8426
_journal_page_last               8448
_journal_paper_doi               10.1021/acs.joc.8b01063
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C6 H10 N O, C4 H5, 2(C6 H5)'
_chemical_formula_sum            'C22 H25 N O'
_chemical_formula_weight         319.43
_chemical_name_systematic
2-methyl-1,3-diphenylcyclopropyl)(piperidin-1-yl)methanone
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-20
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.217(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.6234(2)
_cell_length_b                   18.9368(9)
_cell_length_c                   14.2130(6)
_cell_measurement_reflns_used    6094
_cell_measurement_temperature    149.8(3)
_cell_measurement_theta_max      75.1030
_cell_measurement_theta_min      3.8380
_cell_volume                     1777.85(13)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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      149.8(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2529
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.980
_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   -116.00 -17.00   1.00    2.00    --  -41.60 -38.00 -60.00   99
  2  \w     23.00  98.00   1.00    2.00    --   41.60-125.00 120.00   75
  3  \w      1.00 122.00   1.00    2.00    --   41.60  19.00  90.00  121
  4  \w     31.00 136.00   1.00   26.00    --  107.59 -30.00-180.00  105
  5  \w     25.00 109.00   1.00   26.00    --  107.59 -94.00   0.00   84
  6  \w     94.00 178.00   1.00   26.00    --  107.59 125.00-120.00   84
  7  \w     35.00 133.00   1.00   26.00    --  107.59 -45.00  90.00   98
  8  \w     35.00 133.00   1.00   26.00    --  107.59 -45.00 -60.00   98
  9  \w     35.00 137.00   1.00   26.00    --  107.59 -61.00 -30.00  102
 10  \w   -114.00 -13.00   1.00    2.00    --  -41.60 -57.00-180.00  101
 11  \w      1.00  38.00   1.00    2.00    --   41.60 -99.00 -90.00   37
 12  \w     57.00  83.00   1.00   26.00    --  112.00 178.00-180.00   26
 13  \w     86.00 114.00   1.00   26.00    --  112.00  77.00 -90.00   28
 14  \w    131.00 160.00   1.00   26.00    --  112.00  77.00 -90.00   29
 15  \w     54.00  85.00   1.00   26.00    --  112.00-108.00  -5.00   31
 16  \w     36.00  75.00   1.00   26.00    --  112.00 -94.00 -90.00   39
 17  \w    113.00 139.00   1.00   26.00    --  112.00 111.00-150.00   26
 18  \w    142.00 172.00   1.00   26.00    --  112.00 111.00-150.00   30
 19  \w     50.00 107.00   1.00   26.00    --  112.00 -94.00   0.00   57
 20  \w    127.00 153.00   1.00   26.00    --  112.00 111.00-120.00   26
 21  \w     84.00 109.00   1.00   26.00    --  112.00 -94.00  60.00   25
 22  \w     51.00  77.00   1.00   26.00    --  112.00 -77.00-150.00   26
 23  \w    -62.00 -37.00   1.00    2.00    --  -41.60 108.00  91.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0257325000
_diffrn_orient_matrix_UB_12      0.0579983000
_diffrn_orient_matrix_UB_13      0.0741503000
_diffrn_orient_matrix_UB_21      -0.0523944000
_diffrn_orient_matrix_UB_22      0.0537362000
_diffrn_orient_matrix_UB_23      -0.0794662000
_diffrn_orient_matrix_UB_31      -0.2258230000
_diffrn_orient_matrix_UB_32      -0.0190822000
_diffrn_orient_matrix_UB_33      0.0016931000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0392
_diffrn_reflns_av_unetI/netI     0.0292
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            14190
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.977
_diffrn_reflns_theta_min         3.895
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.556
_exptl_absorpt_correction_T_max  0.956
_exptl_absorpt_correction_T_min  0.841
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    1.193
_exptl_crystal_description       prism
_exptl_crystal_F_000             688
_exptl_crystal_recrystallization_method
'Compound was recrystallized from EtOAc-Hex mixture'
_exptl_crystal_size_max          0.475
_exptl_crystal_size_mid          0.195
_exptl_crystal_size_min          0.083
_refine_diff_density_max         0.187
_refine_diff_density_min         -0.210
_refine_diff_density_rms         0.036
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.142
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     322
_refine_ls_number_reflns         3638
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.142
_refine_ls_R_factor_all          0.0667
_refine_ls_R_factor_gt           0.0587
_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^)+(0.0456P)^2^+0.6787P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1394
_refine_ls_wR_factor_ref         0.1451
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3153
_reflns_number_total             3638
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01063_si_002.cif
_cod_data_source_block           anna_29092017_ae423_8_cr
_cod_database_code               4035577
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C11 H10 N O'
_reflns_odcompleteness_completeness 99.26
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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. Others
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=1-FVAR(1)
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=FVAR(1)
 Sof(C5)=Sof(H5)=1-FVAR(2)
 Sof(C4)=Sof(H4)=FVAR(2)
 Sof(C3)=1-FVAR(3)
 Sof(C2)=FVAR(3)
 Sof(C10)=Sof(C32)=Sof(H32)=Sof(C30)=Sof(H30)=Sof(C28)=Sof(H28)=Sof(C26)=
 Sof(H26)=Sof(C24)=Sof(H24)=1-FVAR(4)
 Sof(C11)=Sof(C33)=Sof(H33)=Sof(C31)=Sof(H31)=Sof(C29)=Sof(H29)=Sof(C27)=
 Sof(H27)=Sof(C25)=Sof(H25)=FVAR(4)
 Sof(C12)=Sof(C23)=Sof(H23)=Sof(C21)=Sof(H21)=Sof(C19)=Sof(H19)=Sof(C17)=
 Sof(H17)=Sof(C15)=Sof(H15)=1-FVAR(5)
 Sof(C13)=Sof(C22)=Sof(H22)=Sof(C20)=Sof(H20)=Sof(C18)=Sof(H18)=Sof(C16)=
 Sof(H16)=Sof(C14)=Sof(H14)=FVAR(5)
 Sof(C7B)=1-FVAR(6)
 Sof(C7A)=FVAR(6)
 Sof(H1A)=1-FVAR(7)
 Sof(H1B)=FVAR(7)
3.a Ternary CH refined with riding coordinates:
 C1(H1A), C1(H1B), C4(H4), C5(H5)
3.b Secondary CH2 refined with riding coordinates:
 C34(H34A,H34B), C35(H35A,H35B), C38(H38A,H38B), C37(H37A,H37B), C36(H36A,H36B)
3.c Aromatic/amide H refined with riding coordinates:
 C33(H33), C31(H31), C29(H29), C27(H27), C25(H25), C22(H22), C20(H20),
 C18(H18), C16(H16), C14(H14), C32(H32), C30(H30), C28(H28), C26(H26), C24(H24),
  C23(H23), C21(H21), C19(H19), C17(H17), C15(H15)
3.d Fitted hexagon refined as free rotating group:
 C11(C33,C31,C29,C27,C25), C13(C22,C20,C18,C16,C14), C10(C32,C30,C28,C26,C24),
 C12(C23,C21,C19,C17,C15)
3.e Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C)
;
_shelx_res_checksum              80860
_shelx_hkl_checksum              86258
_olex2_exptl_crystal_mounting_method
'Mounted on the glass stick by acrylic glue'
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 2.864
_oxdiff_exptl_absorpt_empirical_full_min 0.594