酶催化的卡宾和氮宾转移反应PPT.pptx

酶催化的卡宾和氮宾转移反应
相关的综述：
Huimin Zhao. Current Opinion in Chemical Biolog. 2018, 43, 1–7.
Frances H Arnold. Current panation：
Frances H Arnold & Eric M Chemical Biology 2013. 9, 485–487
TTN有较大提高
Carbene Chemistry
21
Cyclopropanation：
Frances H Arnold. Angew. Chem. Int. Ed. 2014, 53 , 6810 –6813
Four variants, T268A-axX (where “X” denotes the single-letter amino acid code of each axial variant), were expressed as the His-tagged heme domains and purified and characterized by UV/Vis spectroscopy.
在体外用作分离的蛋白质或复合物。
Carbene Chemistry
22
Cyclopropanation：
Frances H Arnold. Angew. Chem. Int. Ed. 2014, 53 , 6810 –6813
Carbene Chemistry
23
Cyclopropanation：
Eric M. Brustad and Albert A. Bowers. ACS Chem. Biol. 2017, 12, 1726−1731
Carbene Chemistry
24
Cyclopropanation：
Rudi Fasan. Angew. Chem. Int. Ed. 2015, 54, 1744 –1748. J Am Chem Soc. 2017, 139, 5293-5296. Angew Chem Int Ed Engl. 2016, 55,16110-16114. ACS Catal. 2016, 6, 7810-7813.
肌红蛋白变体
up to 1095 TON
% ee
R1 = Ar
up to 1110 TON
% ee
up to 95 TON
98% ee
含杂原子芳环
应用
Carbene Chemistry
25
N-H insertion
Frances H. Arnold. Chem Sci. 2014, 5, 598-601. Rudi Fasan. Chem Commun (Camb). 2015, 51, 1532-1534.
P450变体
肌红蛋白变体
26
S-H insertion
Carbene Chemistry
Rudi Fasan. Chem Sci. 2015, 6, 2488-2494.
肌红蛋白变体
27
Carbene Chemistry
Si-H insertion
Frances H. Arnold. Science. 2016, 354, 1048-1051.
28
Carbene Chemistry
Si-H insertion
Frances H. Arnold. Science. 2016, 354, 1048-1051.
29
Doyle-kirmse reaction
Rudi Fasan. Angew Chem Int Ed 2016, 55, 13562-13566.
肌红蛋白变体
Carbene Chemistry
多伊尔-克姆塞反应
30
Doyle-kirmse reaction
Carbene Chemistry
31
Doyle-kirmse reaction
Rudi Fasan. Angew Chem Int Ed 2016, 55, 13562-13566.
Carbene Chemistry
32
Aldehyde olefination
Rudi Fasan. Angew Chem Int Ed. 2016, 55, 2512-2516.
肌红蛋白变体
Carbene Chemistry
33
Aldehyde olefination
Rudi Fasan. Angew Chem Int Ed. 2016, 55, 2512-2516.
重排
Carbene C