Copper(I) Iodide-Catalyzed Asymmetric Synthesis of Optically Active Tertiary α-Allenols

Qi Liu; Tao Cao; Yulin Han; Xingguo Jiang; Yang Tang; Yizhan Zhai; Shengming Ma

doi:10.1055/s-0037-1611641

Synlett, Table of Contents

CC BY ND NC 4.0 · Synlett 2019; 30(04): 477-482
DOI: 10.1055/s-0037-1611641

letter

Copyright with the author

Copper(I) Iodide-Catalyzed Asymmetric Synthesis of Optically Active Tertiary α-Allenols

Qi Liu

^aState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China

^bUniversity of Chinese Academy of Sciences, Beijing 100049, P. R. of China

,

Tao Cao

^aState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China

^bUniversity of Chinese Academy of Sciences, Beijing 100049, P. R. of China

,

Yulin Han

^aState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China

^bUniversity of Chinese Academy of Sciences, Beijing 100049, P. R. of China

,

Xingguo Jiang

^aState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China

^bUniversity of Chinese Academy of Sciences, Beijing 100049, P. R. of China

,

Yang Tang

^aState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China

^bUniversity of Chinese Academy of Sciences, Beijing 100049, P. R. of China

,

Yizhan Zhai

^aState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China

^bUniversity of Chinese Academy of Sciences, Beijing 100049, P. R. of China

,

Shengming Ma *

^aState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China

^cResearch Center for Molecular Recognition and Synthesis, Department of Chemistry, Fudan University, 220 Handan Lu, Shanghai 200433, P. R. of China Email: masm@sioc.ac.cn

› Author Affiliations

Abstract

All articles of this category

Published as part of the 30 Years SYNLETT – Pearl Anniversary Issue

Abstract

A facile CuI-catalyzed asymmetric synthesis of chiral tertiary α-allenols with up to 95% ee starting from common tertiary propargylic alcohols and aldehydes has been developed. The amount of chiral ligand used in this transformation can be as low as 2.5 mol%.

Key words

copper catalysis - asymmetric synthesis - allenols - propargylic alcohols - aldehydes

Full Text

References

References and Notes

1a Modern Allene Chemistry . Vols. 1 and 2. Krause N, Hashmi AS. K. Wiley-VCH; Weinheim: 2004

For a review on allenes in natural products and drugs, see:

1b Hoffmann-Röder A, Krause N. Angew. Chem. Int. Ed. 2004; 43: 1196

For a review on allenes in molecular materials, see:

1c Rivera-Fuentes P, Diederich F. Angew. Chem. Int. Ed. 2012; 51: 2818

For selected reviews on synthetic application of allenes, see:

2a Zimmer R, Dinesh CU, Nandanan E, Khan FA. Chem. Rev. 2000; 100: 3067
2b Hashmi AS. K. Angew. Chem. Int. Ed. 2000; 39: 3590
2c Ma S. Acc. Chem. Res. 2003; 36: 701
2d Brandsma L, Nedolya NA. Synthesis 2004; 735
2e Ma S. Chem. Rev. 2005; 105: 2829
2f Ma S. Aldrichimica Acta 2007; 40: 91
2g Kim H, Williams LJ. Curr. Opin. Drug Discovery Dev. 2008; 11: 870
2h Ma S. Acc. Chem. Res. 2009; 42: 1679
2i Aubert C, Fensterbank L, Garcia P, Malacria M, Simonneau A. Chem. Rev. 2011; 111: 1954
2j Krause N, Winter C. Chem. Rev. 2011; 111: 1994
2k Yu S, Ma S. Angew. Chem. Int. Ed. 2012; 51: 3074
2l Alcaide B. Almendros P. Progress in Allene Chemistry, Chem. Soc. Rev. 2014; 43: 2879
2m Ye J, Ma S. Acc. Chem. Res. 2014; 47: 989
2n Muratore ME, Homs A, Obradors C, Echavarren AM. Chem. Asian J. 2014; 9: 3066
2o Neff RK, Frantz DE. Tetrahedron 2015; 71: 7
2p Alonso JM, Quirós MT, Muñoz MP. Org. Chem. Front. 2016; 3: 1186
2q Santhoshkumar R, Cheng C.-H. Asian J. Org. Chem. 2018; 7: 1151

For recent reviews on the asymmetric synthesis of allenes, see:

3a Ogasawara M. Tetrahedron: Asymmetry 2009; 20: 259
3b Neff RK, Frantz DE. ACS Catal. 2014; 4: 519
3c Ye J, Ma S. Org. Chem. Front. 2014; 1: 1210
3d Chu W, Zhang Y, Wang J. Catal. Sci. Technol. 2017; 7: 4570

For selected recent reports on the asymmetric synthesis of allenes, see:

4a Dai J, Duan X, Zhou J, Fu C, Ma S. Chin. J. Chem. 2018; 36: 387
4b Trost BM, Zell D, Hohn C, Mata G, Maruniak A. Angew. Chem. Int. Ed. 2018; 57: 12916
4c Poulsen PH, Li Y, Lauridsen VH, Jørgensen DK. B, Palazzo TA, Meazza M, Jørgensen KA. Angew. Chem. Int. Ed. 2018; 57: 10661
4d Armstrong RJ, Nandakumar M, Dias RM. P, Noble A, Myers EL, Aggarwal VK. Angew. Chem. Int. Ed. 2018; 57: 8203
4e Huang Y, Pozo J, Torker S, Hoveyda AH. J. Am. Chem. Soc. 2018; 140: 2643
4f Zhang W, Ma S. Chem. Eur. J. 2017; 23: 8590
4g Jiang Y, Diagne AB, Thomson RJ, Schaus SE. J. Am. Chem. Soc. 2017; 139: 1998
4h Qian D, Wu L, Lin Z, Sun J. Nat. Commun. 2017; 8: 567
4i Tap A, Blond A, Wakchaure VN, List B. Angew. Chem. Int. Ed. 2016; 55: 8962
4j Liu Y, Liu X, Hu H, Guo J, Xia Y, Lin L, Feng X. Angew. Chem. Int. Ed. 2016; 55: 4054
4k Chu W.-D, Zhang L, Zhang Z, Zhou Q, Mo F, Zhang Y, Wang J. J. Am. Chem. Soc. 2016; 138: 14558
4l Tang Y, Chen Q, Liu X, Wang G, Lin L, Feng X. Angew. Chem. Int. Ed. 2015; 54: 9512
4m Wang M, Liu Z.-L, Zhang X, Tian P.-P, Xu Y.-H, Loh T.-P. J. Am. Chem. Soc. 2015; 137: 14830
4n Huang X, Cao T, Han Y, Jiang X, Lin W, Zhang J, Ma S. Chem. Commun. 2015; 51: 6956
4o Crouch IT, Neff RK, Frantz DE. J. Am. Chem. Soc. 2013; 135: 4970
4p Wang Y, Zhang W, Ma S. J. Am. Chem. Soc. 2013; 135: 11517
4q Hashimoto T, Sakata K, Tamakuni F, Dutton MJ, Maruoka K. Nat. Chem. 2013; 5: 240
4r Ye J, Fan W, Ma S. Chem. Eur. J. 2013; 19: 716
4s Qian H, Yu X, Zhang J, Sun J. J. Am. Chem. Soc. 2013; 135: 18020
4t Li H, Müller D, Guénée L, Alexakis A. Org. Lett. 2012; 14: 5880
4u Deska J, del Pozo Ochoa C, Bäckvall J.-E. Chem. Eur. J. 2010; 16: 4447
4v Nishimura T, Makino H, Nagaosa M, Hayashi T. J. Am. Chem. Soc. 2010; 132: 12865
4w Ogasawara M, Ikeda H, Nagano T, Hayashi T. J. Am. Chem. Soc. 2001; 123: 2089

5a Ye J, Li S, Chen B, Fan W, Kuang J, Liu J, Liu Y, Miao B, Wan B, Wang Y, Xie X, Yu Q, Yuan W, Ma S. Org. Lett. 2012; 14: 1346
5b Zhang J, Ye J, Ma S. Org. Biomol. Chem. 2015; 13: 4080

6 Knöpfel TF, Aschwanden P, Ichikawa T, Watanabe T, Carreira EM. Angew. Chem. Int. Ed. 2004; 43: 5971
7 Kuang J, Luo H, Ma S. Adv. Synth. Catal. 2012; 354: 933
8 Due to the difficulty of isolating (R)-4, the structures of (R)-4 were assigned by comparison with the structure of (R)-4aa. The NMR yields of (R)-4 were determined by ¹H NMR analysis of the crude reaction mixture. The characteristic peak of (R)-4 appeared at about δ = 3.20–2.90 ppm.

For selected reports that the metal/ligand ratio affects the outcome of catalytic asymmetric reactions, see:

9a Rasappan R, Hager M, Gissibl A, Reiser O. Org. Lett. 2006; 8: 6099
9b Shao Z, Wang J, Ding K, Chan AS. C. Adv. Synth. Catal. 2007; 349: 2375
9c Bélanger É, Houzé C, Guimond N, Cantin K, Paquin J.-F. Chem. Commun. 2008; 3251
9d Schätz A, Rasappan R, Hager M, Gissibl A, Reiser O. Chem. Eur. J. 2008; 14: 7259
9e Peng F, Shao Z, Chan AS. C. Tetrahedron: Asymmetry 2010; 21: 465
9f Zhao C, Seidel D. J. Am. Chem. Soc. 2015; 137: 4650
9g Chen Q, Tang Y, Huang T, Liu X, Lin L, Feng X. Angew. Chem. Int. Ed. 2016; 55: 5286

10 1-[(1S)-4-Methylpenta-1,2-dien-1-yl]cyclohexanol [(S)-3ab]; Typical ProcedureA flame-dried Schlenk tube with a poly(tetrafluoroethylene) plug was charged with CuI (19.1 mg, 0.1 mmol), (R,S _a)-N-PINAP (14.1 mg, 0.025 mmol), and 1,4-dioxane (5 mL) under argon, and the mixture was stirred at r.t. for 30 min. Propargylic alcohol 1a (123.7 mg, 1 mmol)/1,4-dioxane (1 mL), aldehyde 2b (115.8 mg, 1.6 mmol)/1,4-dioxane (1 mL), and azocane (161.9 mg, 1.4 mmol)/1,4-dioxane (1 mL) were then added sequentially under argon. The mixture was then stirred at r.t. until the reaction was complete (TLC, ~1 h). The Schlenk tube was then placed in a preheated oil bath at 130 °C with stirring. After 8 h, the crude mixture was diluted with Et₂O (10 mL) and washed with 3 M aq HCl (10 mL). The organic layer was separated, and the aqueous layer was extracted with Et₂O (2 x 10 mL). The combined organic layer was washed with brine, dried (Na₂SO₄), filtered, and concentrated to give a residue that was purified by chromatography [silica gel, PE–EtOAc (20:1)] to give a liquid; yield: 97.0 mg (54%, 92% ee); [α]_D ²⁸ +80.8 (c 1.005, CHCl₃).HPLC [Chiralcel AD-H column, hexane–i-PrOH (95:5), 0.5 mL/min, λ = 214 nm]: t _R(major) = 11.8 min; t _R(minor) = 10.9 min. IR (neat): 3343, 2958, 2927, 2859, 1961, 1598, 1494, 1463, 1446, 1410, 1380, 1360, 1345, 1318, 1297, 1246, 1192, 1176, 1163, 1146, 1112, 1088, 1058, 1038 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 5.38-5.30 (m, 2 H, CH=C=CH), 2.41-2.27 (m, 1 H, CH), 1.79-1.41 (m, 10 H, protons from 5 × CH₂ + OH), 1.40–1.25 (m, 1 H, proton from CH₂), 1.030 (d, J = 6.8 Hz, 3 H, CH₃), 1.026 (d, J = 6.4 Hz, 3 H, CH₃). ¹³C NMR (100 MHz, CDCl₃): δ = 199.6, 102.3, 101.6, 70.5, 38.4, 38.3, 27.9, 25.5, 22.51, 22.47, 22.4. MS (EI): m/z (%) = 180 (M⁺, 1.51), 99 (100). HRMS: m/z [M⁺] calcd for C₁₂H₂₀O: 180.1514; found: 180.1512.

11a Lowe G. Chem. Commun. 1965; 411
11b Brewster JH. Top. Stereochem. 1967; 2: 1

Supplementary Material

Supporting Information