sp 3 C-H Alkylation with Olefins Yan Xu Dec. 3, 2014
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1 sp 3 C-H Alkylation with Olefins, Yan Xu Dec. 3, 2014
2 1) sp 3 C-H Alkylation via Directed C-H activation 2) Hydroaminoalkylation (still via C-H activation) 3) Hydrohydroxyalkylation (via radical chemistry) 4) Hydrohydroxyalkylation (via transfer hydrogenation chemistry)
3 1) sp 3 C-H Alkylation via Directed C-H activation Rare-earch-metal-philic DG Allylic C-H bond alkylation (double bond as DG) Pyridine type DG 2) Hydroaminoalkylation (still via C-H activation) 3) Hydrohydroxyalkylation (via radical chemistry) 4) Hydrohydroxyalkylation (via transfer hydrogenation chemistry)
4 1) sp 3 C-H Alkylation via Directed C-H activation Rare-earch-metal-philic DG Allylic C-H bond alkylation (double bond as DG) Pyridine type DG 2) Hydroaminoalkylation (still via C-H activation) 3) Hydrohydroxyalkylation (via radical chemistry) 4) Hydrohydroxyalkylation (via transfer hydrogenation chemistry) Yong-Qiang Tu, Angew. Chem. Int. Ed. 2009, 48, 8761
5 1) sp 3 C-H Alkylation via Directed C-H activation Rare-earch-metal-philic DG Allylic C-H bond alkylation (double bond as DG) Pyridine type DG 2) Hydroaminoalkylation (still via C-H activation) 3) Hydrohydroxyalkylation (via radical chemistry) 4) Hydrohydroxyalkylation (via transfer hydrogenation chemistry) Michael J. Krische, Science. 2012, 336, 324
6 sp 3 C-H Alkylation with Olefins Through C-H activation, Yan Xu Dec. 3, 2014
7 1) sp 3 C-H Alkylation via Directed C-H activation Rare-earch-metal-philic DG Allylic C-H bond alkylation (double bond as DG) Pyridine type DG 2) Hydroaminoalkylation (still via C-H activation)
8 Rare-earth metal: Strong oxophilicity High activity of rare-earth alkyl species toward olefin Zhaomin Hou, ACIE. 2012, 51,
9 Rare-earth metal: Strong oxophilicity High activity of rare-earth alkyl species toward olefin Zhaomin Hou, ACIE. 2012, 51,
10 Zhaomin Hou, ACIE. 2012, 51, Olefin: must be terminal Ethylene: oligomer
11 Zhaomin Hou, ACIE. 2012, 51, Olefin: must be terminal Ethylene: oligomer
12 Zhaomin Hou, ACIE. 2012, 51, Olefin: must be terminal Ethylene: oligomer
13 Zhaomin Hou, ACIE. 2013, 52, 4418
14 Zhaomin Hou, ACIE. 2013, 52, 4418
15 Zhaomin Hou, ACIE. 2013, 52, 4418
16 Zhaomin Hou, ACIE. 2013, 52, 4418
17 KIE = 3.7
18
19 KIE = 3.7
20 KIE = 3.7
21 non-reactive substrates: cis/trans-2-butene, 1-hexene, 1-butene, 2-methylpropene, norbornylene, and 2-butyne T. Don Tilley J. Am. Chem. Soc., 2003, 125, 7971
22 Zhi-Xiang Yu, JACS. 2010, 132, 4542
23 Zhi-Xiang Yu, JACS. 2010, 132, 4542
24 Zhi-Xiang Yu, JACS. 2010, 132, 4542
25 Zhi-Xiang Yu, ACIE. 2011, 50, 2144 Bis-allylic Rh complex facilitate the reductive elimination Diene coordination disfavored the double-bond isomerization Zhi-Xiang Yu, Organometallics, 2012, 31, 5185
26 Zhi-Xiang Yu, ACIE. 2011, 50, 2144 Bis-allylic Rh complex facilitate the reductive elimination Diene coordination disfavored the double-bond isomerization Zhi-Xiang Yu, Organometallics, 2012, 31, 5185
27 Zhi-Xiang Yu, ACIE. 2011, 50, 2144 Bis-allylic Rh complex facilitate the reductive elimination Diene coordination disfavored the double-bond isomerization Zhi-Xiang Yu, Organometallics, 2012, 31, 5185
28 95% Chul-Ho Jun Chem. Commun., 1998, 1405
29 95% Chul-Ho Jun Chem. Commun., 1998, 1405
30 Chul-Ho Jun Chem. Commun., 1998, 1405
31
32 Shinji Murai J. Am. Chem. Soc., 2001, 123, 10935
33 Shinji Murai J. Am. Chem. Soc., 2001, 123, 10935
34 Shinji Murai J. Am. Chem. Soc., 2001, 123, 10935
35
36 Olefin part substrate scope is similar as Jun s Shinji Murai J. Am. Chem. Soc., 2001, 123, 10935
37 Shinji Murai J. Am. Chem. Soc., 2001, 123, 10935
38 Shinji Murai J. Am. Chem. Soc., 2001, 123, 10935
39 1) H/D exchange experiment provided good evidence for the reversibility of C-H bonds between substrates and reactants (alkenes), indicating that the cleavage of C-H bonds is not the rate-determining step 2) Shinji Murai J. Am. Chem. Soc., 2001, 123, 10935
40 Bert U. W. Maes Chem. Eur. J. 2012, 18, 10393
41 Bert U. W. Maes Chem. Eur. J. 2012, 18, 10393
42 Bert U. W. Maes Chem. Eur. J. 2012, 18, 10393
43 Bert U. W. Maes Chem. Eur. J. 2012, 18, 10393
44 carboxylic acid / alcohol has a significant effect on catalyst initiation Bert U. W. Maes Chem. Eur. J. 2012, 18, 10393
45 Bert U. W. Maes Chem. Eur. J. 2012, 18, 10393
46 Bert U. W. Maes Adv. Synth. Catal. 2014, 356, 1610
47 [Ru] = (PCy 3 ) 2 (CO)RuHCl Chae S. Yi Organometallics 2004, 23, 5392
48 1 = (PCy 3 ) 2 (CO)RuHCl 1) catalytic active 2) k NH /k ND = 1.9 (consistent with a rate-limiting N-H bond activation step) Chae S. Yi Organometallics 2004, 23, 5392
49 Takanori Shibata Org. Lett., 2011, 13, 4692
50 For substrate scope: R = Me, Et Olefin = styrene, diene, ee = 61-90% terminal olefin s yield is low Takanori Shibata Org. Lett., 2011, 13, 4692
51 For substrate scope: R = Me, Et Olefin = styrene, diene, ee = 61-90% terminal olefin s yield is low Takanori Shibata Org. Lett., 2011, 13, 4692
52 Takanori Shibata Tetrahedron 68 (2012) 9009
53 Reaction condition: Acrylate, Vinylsilane (DME, 85 ) Styrene, vinylboronic ester, 1-hexene (DME, 140 ) better substrate scope 63% 42% 64% Till Opatz Org. Lett., 2014, 16, 4201
54 Reaction condition: Acrylate, Vinylsilane (DME, 85 ) Styrene, vinylboronic ester, 1-hexene (DME, 140 ) better substrate scope 63% 42% 64% Till Opatz Org. Lett., 2014, 16, 4201
55 60 % 46 % Dalibor Sames J. Am. Chem. Soc., 2004, 126, 6556
56 60 % 46 % Dalibor Sames J. Am. Chem. Soc., 2004, 126, 6556
57 60 % 46 % Dalibor Sames J. Am. Chem. Soc., 2004, 126, 6556
58 Kinetic competent and chemical competent catalyst Dalibor Sames J. Am. Chem. Soc., 2004, 126, 6556
59 Guangbin Dong, Science 2014, 345, 68
60 1) sp 3 C-H Alkylation via Directed C-H activation Rare-earch-metal-philic DG Allylic C-H bond alkylation (double bond as DG) Pyridine type DG 2) Hydroaminoalkylation (still via C-H activation)
61 1) sp 3 C-H Alkylation via Directed C-H activation Rare-earch-metal-philic DG Allylic C-H bond alkylation (double bond as DG) Pyridine type DG 2) Hydroaminoalkylation (still via C-H activation)
62 toluene, 200 o C, 150h * Isolated by distillation Maspero, F. Synthesis 1980, 305.
63 yield not given The activity of the various metal amides for this reaction roughly parallels their efficacy for H-D exchange Nugent, W. A Organometallics 1983, 2, 161
64 yield not given The activity of the various metal amides for this reaction roughly parallels their efficacy for H-D exchange Nugent, W. A Organometallics 1983, 2, 161
65 Nugent, W. A Organometallics 1983, 2, 161 zirconocene-η 2 -imine complexes was formed faster from N-alkyl arylamido complexes than from dialkylamido complexes. Organometallics 1994, 13, 190 John Hartwig J. Am. Chem. Soc., 2007, 129, 6690
66 Nugent, W. A Organometallics 1983, 2, 161 zirconocene-η 2 -imine complexes was formed faster from N-alkyl arylamido complexes than from dialkylamido complexes. Organometallics 1994, 13, 190 John Hartwig J. Am. Chem. Soc., 2007, 129, 6690
67 Cannot use styrene and 1,2-disubstituted olefin John Hartwig J. Am. Chem. Soc., 2007, 129, 6690
68 John Hartwig J. Am. Chem. Soc., 2008, 130, 14940
69 John Hartwig J. Am. Chem. Soc., 2008, 130, 14940
70 John Hartwig J. Am. Chem. Soc., 2008, 130, 14940
71 John Hartwig J. Am. Chem. Soc., 2008, 130, 14940
72 Sven Doye Angew. Chem. Int. Ed. 2009, 48, 1153
73 Sven Doye Angew. Chem. Int. Ed. 2009, 48, 1153
74 Sven Doye Angew. Chem. Int. Ed. 2009, 48, 1153
75 Sven Doye Angew. Chem. Int. Ed. 2009, 48, 1153
76 Sven Doye Angew. Chem. Int. Ed. 2009, 48, 1153
77 Sven Doye Angew. Chem. Int. Ed. 2009, 48, 1153 [Ti(Bn) 4 ] Slightly enhanced activity First addition to styrene: 30% yield, 1:1 branch:linear Sven Doye ChemCatChem 2009, 1, 162
78 Sven Doye Angew. Chem. Int. Ed. 2009, 48, 1153 [Ti(Bn) 4 ] Slightly enhanced activity First addition to styrene: 30% yield, 1:1 branch:linear Sven Doye ChemCatChem 2009, 1, 162
79 Laurel L. Schafer J. Am. Chem. Soc., 2009, 131, 2116
80 Laurel L. Schafer J. Am. Chem. Soc., 2009, 131, 2116
81 Zr: larger metal center 2-pyridonate ligand: less sterically demanding
82 Zr: larger metal center 2-pyridonate ligand: less sterically demanding
83
84
85 Laurel L. Schafer Angew. Chem. Int. Ed. 2009, 48, 8361
86 1 Laurel L. Schafer Angew. Chem. Int. Ed. 2009, 48, 8361
87 Laurel L. Schafer Angew. Chem. Int. Ed. 2009, 48, 8361
88 Laurel L. Schafer Angew. Chem. Int. Ed. 2009, 48, % R = Ph 68% R = Me 43% See: Org. Lett., 2013, 15, 2182
89 For further improvement, See: Guofu Zi, Chem. Commun., 2010, 46, 6296 Guofu Zi, Dalton. Trans., 2011, 40, 1547 Laurel L. Schafer Angew. Chem. Int. Ed. 2009, 48, 8361
90 Only 105 o C: is this catalyst able to solve the styrene problem? Sven Doye Angew. Chem. Int. Ed. 2009, 48, 1153 Sven Doye Angew. Chem. Int. Ed. 2010, 49, 2626
91 Only 105 o C: is this catalyst able to solve the styrene problem? Sven Doye Angew. Chem. Int. Ed. 2009, 48, 1153 Sven Doye Angew. Chem. Int. Ed. 2010, 49, 2626
92 Sven Doye Angew. Chem. Int. Ed. 2010, 49, 2626
93 Sven Doye Chem. Eur. J. 2013, 19, 3833 Sven Doye Angew. Chem. Int. Ed. 2010, 49, 2626
94 Sven Doye, Angew. Chem. Int. Ed. 2011, 50, 6401
95 Zero-order rate dependence on aminoalkene Sven Doye, Angew. Chem. Int. Ed. 2011, 50, 6401
96 Zero-order rate dependence on aminoalkene Sven Doye, Angew. Chem. Int. Ed. 2011, 50, 6401
97 k obs (1-H)/k obs (1-D) = 7.3 at 130 o C with 5 mol% and 10 mol% [Ti(NMe 2 ) 4 ] Zero-order rate dependence on aminoalkene Sven Doye, Angew. Chem. Int. Ed. 2011, 50, 6401
98 k obs (1-H)/k obs (1-D) = 7.3 at 130 o C with 5 mol% and 10 mol% [Ti(NMe 2 ) 4 ] Zero-order rate dependence on aminoalkene Sven Doye, Angew. Chem. Int. Ed. 2011, 50, 6401
99 Sven Doye, Angew. Chem. Int. Ed. 2011, 50, 6401
100 59-98% ee 61-95% yield Kai C. Hultzsch J. Am. Chem. Soc., 2012, 134, 3300
101 Non-dissociative Fast reversible r.d.s: Either by amide exchange Or by alkene insertion Catalyst activity can be enhanced by a more electron deficient ligand
102 84% 73% 61% 130 o C 36% 145 o C Styrene disubstituted terminal alkenes internal unstrained alkenes dialkylamines. Laurel L. Schafer Chem. Eur. J. 2013, 19, 8751
103 84% 73% 61% 130 o C 36% 145 o C 16% 145 o C 85% Styrene disubstituted terminal alkenes internal unstrained alkenes dialkylamines. Laurel L. Schafer Chem. Eur. J. 2013, 19, 8751
104 84% 73% 61% 130 o C 36% 145 o C Styrene disubstituted terminal alkenes internal unstrained alkenes dialkylamines. Laurel L. Schafer Chem. Eur. J. 2013, 19, 8751
105 Laurel L. Schafer Chem. Eur. J. 2013, 19, % 73% 61% 130 o C 36% 145 o C Styrene disubstituted terminal alkenes internal unstrained alkenes dialkylamines. Laurel L. Schafer Tetrahedron 2013, 69, 5737
106 minimum temperature required to achieve at least three turnovers within 20 h sufficient steric bulk is critical Electron withdrawing ligand is critical Phosphoramidates increased electronwithdrawing properties tunable steric bulk at both phosphorus and nitrogen Laurel L. Schafer Angew. Chem. Int. Ed. 2013, 52, 9144
107 minimum temperature required to achieve at least three turnovers within 20 h sufficient steric bulk is critical Electron withdrawing ligand is critical Phosphoramidates increased electronwithdrawing properties tunable steric bulk at both phosphorus and nitrogen Laurel L. Schafer Angew. Chem. Int. Ed. 2013, 52, 9144
108 Laurel L. Schafer Angew. Chem. Int. Ed. 2013, 52, 9144
109 Laurel L. Schafer Angew. Chem. Int. Ed. 2013, 52, 9144
110 Laurel L. Schafer Org. Lett., 2013, 15, 6002
111
112
113 e-withdrawing and steric less hindered ligand! Laurel L. Schafer Org. Lett., 2013, 15, 6002 Ta Cl bond [2.4959(8) Å] is significantly longer than Ta NMe2(axial) bond [1.970(3) Å] the bonding the of Ta N amido bond lengths are shorter in 1 than in 2 Improved metal accessibility increased electrophilic nature of the metal center Laurel L. Schafer J. Am. Chem. Soc., 2014, 136 (31), pp 10898
114 Laurel L. Schafer J. Am. Chem. Soc., 2014, 136 (31), pp 10898
115 Laurel L. Schafer J. Am. Chem. Soc., 2014, 136 (31), pp 10898
116 Laurel L. Schafer J. Am. Chem. Soc., 2014, 136 (31), pp 10898
117 Another unsolved problem: Styrene selectivity w/ [Ti] Branched selectivity: has already been achieved by [Ta] a:b>99:1 Eur. J. Org. Chem. 2014, 2790
118 Linear selectivity? Schafer s catalyst for intramaleculor HAA reaction By NMR Sven Doye Angew. Chem. Int. Ed. 2013, 52, 1806
119
120
121 Summary sp 3 C-H alkylation has been achieved via many different machanism Metal: d 0 & d 8 Logical development of ligand and catalyst is critical Inspiration of our own work
122 Summary sp 3 C-H alkylation has been achieved via many different machanism Metal: d 0 & d 8 Logical development of ligand and catalyst is critical Inspiration of our own work
123 The predominance of multiply deuterated products, especially from the Zr catalyst, suggests that further metalation of the intermediate metallacycle is fast compared with the reverse reaction.
124
125
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