Chiral Brønsted Acid-Catalyzed Asymmetric Allyl(propargyl)boration Reaction ofortho-Alkynyl Benzaldehydes: Synthetic Applications and Factors Governing the Enantioselectivity
Rodríguez, Elsa; Grayson, Matthew N.; Asensio, Amparo; Barrio, Pablo; Houk, K. N.; Fustero, Santos; ACS Catalysis 6 (2016) 2506–; doi:10.1021/acscatal.6b00209

data_4513847
_publ_section_title
;
 Chiral Br\/onsted Acid-Catalyzed Asymmetric Allyl(propargyl)boration
 Reaction ofortho-Alkynyl Benzaldehydes: Synthetic Applications and
 Factors Governing the Enantioselectivity
;
_journal_issue                   4
_journal_name_full               'ACS Catalysis'
_journal_page_first              2506
_journal_paper_doi               10.1021/acscatal.6b00209
_journal_volume                  6
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_compound_source        'synthesis as described'
_chemical_formula_moiety         'C18 H14 O1'
_chemical_formula_sum            'C18 H14 O'
_chemical_formula_weight         246.29
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      4
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-10-17T13:44:58-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 97.605(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.5044(2)
_cell_length_b                   4.77080(10)
_cell_length_c                   13.7318(3)
_cell_measurement_reflns_used    8686
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.064
_cell_measurement_theta_min      3.186
_cell_measurement_wavelength     1.54184
_cell_volume                     682.11(2)
_computing_cell_refinement       'CrysAlis Pro (Oxford Diffraction Ltd., 2011)'
_computing_data_collection       'CrysAlis Pro (Oxford Diffraction Ltd., 2011)'
_computing_data_reduction        'CrysAlis Pro (Oxford Diffraction Ltd., 2011)'
_computing_molecular_graphics    'Diamond v.3.2f (Crystal Impact GbR, 2008)'
_computing_publication_material  'WinGX publication routines (Farrugia, 1999)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'OLEX2 (Dolomanov et al, 2009)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2012
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1
_diffrn_measured_fraction_theta_max 1
_diffrn_measurement_details
;
  1 omega  -40.00  -12.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8256  -77.0000 -120.0000 28

  2 omega -115.00  -27.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8256  -57.0000 -150.0000 88

  3 omega -113.00  -87.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8256  -57.0000  -60.0000 26

  4 omega  -57.00  -11.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8256  -57.0000  -60.0000 46

  5 omega  -74.00   38.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8256   77.0000  150.0000 112

  6 omega  -80.00  -51.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -71.0000 -177.2698 29

  7 omega  -77.00  -50.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -76.0000  -67.0624 27

  8 omega  -80.00  -53.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -61.0000  -60.0000 27

  9 omega  -74.00  -49.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000  -60.0000 25

 10 omega  -76.00  -51.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -70.0000  -91.4588 25

 11 omega  -85.00  -51.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -68.0000 -144.2917 34

 12 omega  -74.00  -49.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000 -150.0000 25

 13 omega -161.00 -134.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000 -111.0000 -180.0000 27

 14 omega  -78.00  -50.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -73.0000 -120.3591 28

 15 omega  -77.00  -51.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000  -90.0000 26

 16 omega -123.00  -95.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -70.0000  -91.4588 28

 17 omega  -78.00  -50.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000 -180.0000 28

 18 omega  -71.00  -20.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000   45.0000  -60.0000 51

 19 omega  -76.00  -51.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -71.0000 -107.6376 25

 20 omega  -89.00  -54.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -57.0000 -173.8605 35

 21 omega  -74.00  -49.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000 -120.0000 25

 22 omega   36.00   63.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000 -180.0000 27

 23 omega   86.00  112.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000  -30.0000 26

 24 omega  114.00  143.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000 -120.0000 29

 25 omega   80.00  109.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000 -120.0000 29

 26 omega   39.00   69.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000  150.0000 30

 27 omega  129.00  155.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000 -150.0000 26

 28 omega   85.00  111.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000 -150.0000 26

 29 omega  116.00  150.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000  -30.0000 34

 30 omega   36.00   64.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000   60.0000 28

 31 omega   46.00   77.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000   30.0000 31

 32 omega   84.00  154.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000  -90.0000 70

 33 omega  133.00  158.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000 -150.0000 25

 34 omega   30.00   95.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000  -60.0000 65

 35 omega   79.00  116.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000 -150.0000 37

 36 omega   92.00  119.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000  -60.0000 27

 37 omega   75.00  125.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -61.0000  150.0000 50

 38 omega  121.00  157.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000  -60.0000 36

 39 omega   80.00  118.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000  -60.0000 38

 40 omega   40.00   72.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -61.0000  150.0000 32

 41 omega   39.00   64.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000  -90.0000 25

 42 omega  125.00  156.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000 -180.0000 31

 43 omega   86.00  113.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000  -90.0000 27

 44 omega   85.00  113.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000 -120.0000 28

 45 omega   83.00  118.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000 -180.0000 35

 46 omega  -67.00  -18.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8256  124.0000    3.0000 49

 47 omega   85.00  115.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000   60.0000 30

 48 omega   71.00  104.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000  150.0000 33

 49 omega   51.00  110.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -77.0000  -30.0000 59

 50 omega   36.00   62.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000    0.0000 26

 51 omega   38.00   64.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000   60.0000 26

 52 omega   80.00  134.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -61.0000   30.0000 54

 53 omega  119.00  146.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  111.0000  120.0000 27

 54 omega  -67.00   35.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8256   37.0000    0.0000 102

 55 omega -115.00  -11.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8256  -57.0000   60.0000 104

 56 omega -115.00  -11.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8256  -57.0000    0.0000 104

 57 omega  -67.00   35.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8256   37.0000  -90.0000 102

 58 omega  -98.00   -2.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8256  125.0000  -30.0000 96

 59 omega -115.00  -11.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8256  -57.0000  120.0000 104

 60 omega    7.00  120.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       40.8256   77.0000  -60.0000 113

 61 omega   11.00  115.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       40.8256   57.0000   90.0000 104

 62 omega -162.00  -49.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000   30.0000 113

 63 omega -162.00  -49.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000  120.0000 113

 64 omega   35.00  116.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -111.0000 -180.0000 81

 65 omega   83.00  158.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000   60.0000 75

 66 omega   85.00  158.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000  150.0000 73

 67 omega   85.00  158.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000   30.0000 73

 68 omega   82.00  158.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   30.0000  120.0000 76

 69 omega   29.00   96.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -94.0000    0.0000 67

;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0704781
_diffrn_orient_matrix_UB_12      0.0161572
_diffrn_orient_matrix_UB_13      -0.091407
_diffrn_orient_matrix_UB_21      0.1265409
_diffrn_orient_matrix_UB_22      0.0664968
_diffrn_orient_matrix_UB_23      0.0661845
_diffrn_orient_matrix_UB_31      0.0301911
_diffrn_orient_matrix_UB_32      -0.3154448
_diffrn_orient_matrix_UB_33      0.0092073
_diffrn_radiation_monochromator  'Multilayer optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_source         'Nova (Cu) X-ray micro-source'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0323
_diffrn_reflns_av_unetI/netI     0.0199
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            13241
_diffrn_reflns_theta_full        72.45
_diffrn_reflns_theta_max         72.45
_diffrn_reflns_theta_min         3.25
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.566
_exptl_absorpt_correction_T_max  0.975
_exptl_absorpt_correction_T_min  0.89
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
        CrysAlisPro, Agilent Technologies,
        Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
        (compiled Dec  3 2012,18:21:49)
Analytical numeric absorption correction using a multifaceted crystal
                        model based on expressions derived by R.C. Clark & J.S.
        (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.199
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             260
_exptl_crystal_size_max          0.3688
_exptl_crystal_size_mid          0.0631
_exptl_crystal_size_min          0.046
_refine_diff_density_max         0.157
_refine_diff_density_min         -0.154
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
The Friedel pair coverage of the experiment is almost complete (95%).
Analysis of the absolute structure using likelihood methods
(Hooft, Straver & Spek, 2008) was performed using PLATON (Spek, 2011).
 The results indicated that the absolute structure had been correctly
 assigned. The method calculated that the probability that the structure 
is inverted is smaller than 10-16. The absolute structure parameter y 
(Hooft, Straver & Spek, 2008) was calculated using PLATON (Spek,
2010). The resulting value was y=0.12(10), which together with Flack parameter 
value, indicate that the absolute structure has sureley been determined 
correctly.

Flack, H. D. (1983), Acta Cryst. A39, 876-881
Flack & G. Bernardinelli, Acta Cryst. 1999, A55, 908-915; 
H. D. Flack & G. Bernardinelli, J. Appl. Cryst. 2000, 33, 1143-1148.

R. W. W. Hooft, L. H. Straver & A. L. Spek, J. Appl. Cryst. 2008, 41, 96-103
A. L. Spek (2010) PLATON, Utrecht, The Netherlands; 
A. L. Spek, J. Appl. Cryst. 2003, 36, 7-13
A. L. Thompson & D. J. Watkin, Tetrahedron: Asymmetry 2009, 20, 712--717

;
_refine_ls_abs_structure_Flack   0.1(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    noref
_refine_ls_matrix_type           full
_refine_ls_number_parameters     176
_refine_ls_number_reflns         2623
_refine_ls_number_restraints     11
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0323
_refine_ls_R_factor_gt           0.0309
_refine_ls_shift/su_max          0
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0462P)^2^+0.0988P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0796
_refine_ls_wR_factor_ref         0.0807
_reflns_number_gt                2532
_reflns_number_total             2623
_reflns_threshold_expression     >2\s(I)
_cod_data_source_file            cs6b00209_si_002.cif
_cod_data_source_block           a2014274_er1218_2
_cod_depositor_comments
'Adding full bibliography for 4513846--4513847.cif.'
_cod_database_code               4513847