Page 220 - 《精细化工》2020年第5期
P. 220
·1070· 精细化工 FINE CHEMICALS 第 37 卷
后,充 H 2 至压力 3.0 MPa 反应过夜。停止反应,小 [3] MEHMET D, SEMA A D, HANS-GUENTHER S. Synthesis of
心释放氢气后,经硅藻土过滤后,旋干有机溶剂后, C2-symmetric bisphosphine ligands from tartaric acid, and their
performance in the Pd-catalyzed asymmetric o-allylation of a
得到消旋 1,1′-(4,6-二苯并呋喃二基)双乙基-1-胺(Ⅶ) phenol[J]. European Journal of Organic Chemistry, 2014, 2014(20):
7.5 g,浅黄绿色油状液体,收率 99%。 4315-4326.
[4] DONG C, ALPER H. Catalytic asymmetric cyclo carbonylation
2.3.2.2 消旋体 1,1′-(4,6-二苯并呋喃二基)双乙基 of o-isopropenyl phenols: Enantioselective synthesis of six-membered
-1-胺(Ⅶ)与酸性拆分剂成盐拆分 ring lactones[J]. Journal of Organic Chemistry, 2004, 69(15): 5011-
采用拆分消旋环己双胺的改进方法〔(L)-酒石酸/ 5014.
[5] REETZ M T, NEUGEBAUER T. New diphosphite ligands for
HOAc/MeOH/H 2 O/回流〕对消旋体 1,1′-(4,6-二苯并 catalytic asymmetric hydrogenation: The crucial role of
呋喃二基)双乙基-1-胺进行拆分时 [18] ,过程中无盐析 conformationally enantiomeric diols[J]. Angewandte Chemie
International Edition, 1999, 38(1/2): 179-181.
出。采用等物质的量(R)-扁桃酸或(D)-樟脑磺酸/ (D)-
[6] OU Jun (欧军), CHEN Yixin (陈亿新), LIU Juntao (刘军涛), et al.
二苯甲酰酒石酸/(L)-苹果酸分别在丙酮和甲醇溶剂 Application of chiral diol ligand derived from D-mannitol in
中成盐拆分时,仅在(D)-DBTA 中有发黏固体析出, asymmetric epoxidation reaction[J]. Journal of South China Normal
University Natural Science Edition (华南师范大学学报: 自然科学
过滤干燥后,成盐收率接近 100%。将(D)-DBTA 用 版), 2007, (1): 75-81, 97.
量降至 0.5 mol 时,采用甲醇、乙醇、二氯甲烷、乙 [7] DENG Y, CHANG C J, NOCERA D G. Direct observation of the
醚、乙醇/丙酮、乙醇/乙醚不同溶剂成盐拆分时,均得 “pac-man” effect from dibenzofuran-bridged cofacial bisporphyrins[J].
Journal of the American Chemical Society, 2000, 122(2): 410-411.
到发黏固体,过滤游离后得到产品仍为近乎外消旋 [8] IRELAND B J, WHEATON C A, HAYES P G. Cationic
体。将拆分剂更换为(D)-DTTA 时,取得了类似结果。 organomagnesium complexes as highly active initiators for the
ring-opening polymerization of ε-capro lactone[J]. Organometallics,
3 结论 [9] 2010, 29(5): 1079-1084.
YAN Y, WANG J, KAYSER M. Approaches to the synthesis of
enantiopure α-hydroxy-β-lactams with functionalized side chains[J].
(1)采用二苯并呋喃为原料,在 s-BuLi/TMEDA/ Tetrahedron: Asymmetry, 2007, 18(17): 2021-2029.
CH 3 CHO 条件下反应,打浆纯化得到 1,1′-(4,6-二苯 [10] YOICHIRO K, HIROKAZU U, ATSUSHI K, et al. Rearrangement
of indene skeletons under mild conditions[J]. Journal of Organic
并呋喃二基)双乙基-1-醇(Ⅲa),接着在 PCC 中氧 Chemistry, 2007, 72(18): 6749 -6752.
化,得到 1,1′-(4,6-二苯并呋喃二基)双乙基-1-酮(Ⅳa), [11] KLAUCK M I, PATEL S G, WISKUR S L. Obtaining enriched
随后在(S)-MeCBS/BH 3 -Me 2 S 条件下还原,乙酸乙酯 compounds via a tandem enantioselective reaction and kinetic
resolution polishing sequence[J]. Journal of Organic Chemistry,
重结晶后得到(1R,1′R)-1,1′-(4,6-二苯并呋喃二基)双 2012, 77(7): 3570- 3575.
乙基-1-醇(Ⅰ),无内消旋体。 [12] JIANG Yubo (江玉波), KUANG Chunxiang (匡春香), HAN
Chunmei (韩春美). et al. Advances in the synthesis of organic
(2)(1R,1′R)-1,1′-(4,6-二苯并呋喃二基)双乙基- azides[J]. Chinese Journal of Organic Chemisty (有机化学), 2012,
1-醇(Ⅰ)经过不同浓度下核磁共振氢谱分析,醇羟 32(12): 2231-2238.
基位置不随浓度变化,表明存在一定的分子内氢键。 [13] TELZEROW A, PARIS J, HÅKANSSON M, et al. Amine
transaminase from exophiala xenobiotica—crystal structure and
(3)采用消旋 1,1′-(4,6-二苯并呋喃二基)双乙基- engineering of a fold Ⅳ transaminase that naturally converts biaryl
1-醇(Ⅲa)经过氯化亚砜氯代、叠氮化钠取代和氢 ketones [J]. ACS Catalysis, 2019, 9(2): 1140-1148.
[14] ITO M, KOYAKUMARU K, OHTA T, et al. A simple and
化还原,得到消旋 1,1′-(4,6-二苯并呋喃二基)双乙基
convenient synthesis of alkyl azides under mild conditions [J].
-1-胺(Ⅶ),加入常见手性酸成盐拆分的方法未能得 Synthesis, 1995, 1995(4): 376-378.
到(1S,1′S)-1,1′-(4,6-二苯并呋喃二基)双乙基-1-胺(Ⅷ)。 [15] REN Xinfeng (任新锋), XU Jingli (徐菁利), CHEN Sihao (陈思浩).
Recent progress of mitsunobu reaction[J]. Chinese Journal of
(4)(1R,1′R)-1,1′-(4,6-二苯并呋喃二基)双乙基- Organic Chemisty (有机化学), 2006, 26(4): 454-461.
1-醇(Ⅰ)在经过一定条件磷化时,反应过程中检 [16] LIU Q, ZHOU Y. Synthesis of chiral cyclohexane-backbone P,
测得到了双磷配体,但在柱层析纯化时分解,纯化 N-ligands derived from pyridine and their applications in asymmetric
catalysis[J]. Tetrahedron Letter, 2007, 48(12): 2101-2104.
方法仍需进一步研究。 [17] IRANPOOR N, FIROUZABADI H, AKHLAGHINIA B, et al. A
novel and highly selective conversion of alcohols, thiols, and silyl
参考文献: ethers to azides using the triphenyl phosphine/2, 3-dichloro-5,
6-dicyanobenzoquinone (DDQ)/n-Bu 4NN 3 system[J]. Synthesis, 2004,
[1] BRUNEL Jean-Michel, GERARD B. A new and efficient method for
the resolution of 1,1′-binaphthalene-2,2′-diol[J]. Journal of Organic 45(16): 3291-3294.
Chemistry, 1993, 58(25): 7313-7314. [18] SCHANZ H-J, LINSEIS M A, GILHEANY D G. Improved
[2] ZHOU Y F, WANG R, XU Z Q. et al. Highly enantioselective resolution methods for (R, R)- and (S, S)-cyclohexane-1, 2-diamine
phenylacetylene additions to ketones catalyzed by (S)-BINOL-Ti and (R)- and (S)-BINOL[J]. Tetrahedron Asymmetry, 2003, 14(18):
complex[J]. Organic Letter, 2004, 6(23): 4147-4149. 2763-2769.