Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
Review
. 2020 Feb 12;120(3):1513-1619.
doi: 10.1021/acs.chemrev.9b00414. Epub 2020 Jan 6.

Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C═N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin-Anh and Chelation-Control Models

Nicole D Bartolo  1 , Jacquelyne A Read  1   2 , Elizabeth M Valentín  1   3 , K A Woerpel  1
Affiliations
Review

Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C═N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin-Anh and Chelation-Control Models

Nicole D Bartolo et al. Chem Rev. .

Abstract

This review describes the additions of allylmagnesium reagents to carbonyl compounds and to imines, focusing on the differences in reactivity between allylmagnesium halides and other Grignard reagents. In many cases, allylmagnesium reagents either react with low stereoselectivity when other Grignard reagents react with high selectivity, or allylmagnesium reagents react with the opposite stereoselectivity. This review collects hundreds of examples, discusses the origins of stereoselectivities or the lack of stereoselectivity, and evaluates why selectivity may not occur and when it will likely occur.

PubMed Disclaimer

Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1.
Scheme 1.
Scheme 2.
Scheme 2.
Scheme 3.
Scheme 3.
Scheme 4.
Scheme 4.
Scheme 5.
Scheme 5.
Scheme 6.
Scheme 6.
Scheme 7.
Scheme 7.
Scheme 8.
Scheme 8.
Scheme 9.
Scheme 9.
Scheme 10.
Scheme 10.
Scheme 11.
Scheme 11.
Scheme 12.
Scheme 12.
Scheme 13.
Scheme 13.
Scheme 14.
Scheme 14.
Scheme 15.
Scheme 15.
Scheme 16.
Scheme 16.
Scheme 17.
Scheme 17.
Scheme 18.
Scheme 18.
Scheme 19.
Scheme 19.
Scheme 20.
Scheme 20.
Scheme 21.
Scheme 21.
Scheme 22.
Scheme 22.
Scheme 23.
Scheme 23.
Scheme 24.
Scheme 24.
Scheme 25.
Scheme 25.
Scheme 26.
Scheme 26.
Scheme 27.
Scheme 27.
Scheme 28.
Scheme 28.
Scheme 29.
Scheme 29.
Scheme 30.
Scheme 30.
Scheme 31.
Scheme 31.
Scheme 32.
Scheme 32.
Scheme 33.
Scheme 33.
Scheme 34.
Scheme 34.
Scheme 35.
Scheme 35.
Scheme 36.
Scheme 36.
Scheme 37.
Scheme 37.
Scheme 38.
Scheme 38.
Scheme 39.
Scheme 39.
Scheme 40.
Scheme 40.
Scheme 41.
Scheme 41.
Scheme 42.
Scheme 42.
Scheme 43.
Scheme 43.
Scheme 44.
Scheme 44.
Scheme 45.
Scheme 45.
Scheme 46.
Scheme 46.
Scheme 47.
Scheme 47.
Scheme 48.
Scheme 48.
Scheme 49.
Scheme 49.
Scheme 50.
Scheme 50.
Scheme 51.
Scheme 51.
Scheme 52.
Scheme 52.
Scheme 53.
Scheme 53.
Scheme 54.
Scheme 54.
Scheme 55.
Scheme 55.
Scheme 56.
Scheme 56.
Scheme 57.
Scheme 57.
Scheme 58.
Scheme 58.
Scheme 59.
Scheme 59.
Scheme 60.
Scheme 60.
Scheme 61.
Scheme 61.
Scheme 62.
Scheme 62.
Scheme 63.
Scheme 63.
Scheme 64.
Scheme 64.
Scheme 65.
Scheme 65.
Scheme 66.
Scheme 66.
Scheme 67.
Scheme 67.
Scheme 68.
Scheme 68.
Scheme 69.
Scheme 69.
Scheme 70.
Scheme 70.
Scheme 71.
Scheme 71.
Scheme 72.
Scheme 72.
Scheme 73.
Scheme 73.
Scheme 74.
Scheme 74.
Scheme 75.
Scheme 75.
Scheme 76.
Scheme 76.
Scheme 77.
Scheme 77.
Scheme 78.
Scheme 78.
Scheme 79.
Scheme 79.
Scheme 80.
Scheme 80.
Scheme 81.
Scheme 81.
Scheme 82.
Scheme 82.
Scheme 83.
Scheme 83.
Scheme 84.
Scheme 84.
Scheme 85.
Scheme 85.
Scheme 86.
Scheme 86.
Scheme 87.
Scheme 87.
Scheme 88.
Scheme 88.
Scheme 89.
Scheme 89.
Scheme 90.
Scheme 90.
Scheme 91.
Scheme 91.
Scheme 92.
Scheme 92.
Scheme 93.
Scheme 93.
Scheme 94.
Scheme 94.
Scheme 95.
Scheme 95.
Scheme 96.
Scheme 96.
Scheme 97.
Scheme 97.
Scheme 98.
Scheme 98.
Scheme 99.
Scheme 99.
Scheme 100.
Scheme 100.
Scheme 101.
Scheme 101.
Scheme 102.
Scheme 102.
Scheme 103.
Scheme 103.
Scheme 104.
Scheme 104.
Scheme 105.
Scheme 105.
Scheme 106.
Scheme 106.
Scheme 107.
Scheme 107.
Scheme 108.
Scheme 108.
Scheme 109.
Scheme 109.
Scheme 110.
Scheme 110.
Scheme 111.
Scheme 111.
Scheme 112.
Scheme 112.
Scheme 113.
Scheme 113.
Scheme 114.
Scheme 114.
Scheme 115.
Scheme 115.
Scheme 116.
Scheme 116.
Scheme 117.
Scheme 117.
Scheme 118.
Scheme 118.
Scheme 119.
Scheme 119.
Scheme 120.
Scheme 120.
Scheme 121.
Scheme 121.
Scheme 122.
Scheme 122.
Scheme 123.
Scheme 123.
Scheme 124.
Scheme 124.
Scheme 125.
Scheme 125.
Scheme 126.
Scheme 126.
Scheme 127.
Scheme 127.
Scheme 128.
Scheme 128.
Scheme 129.
Scheme 129.
Scheme 130.
Scheme 130.
Scheme 131.
Scheme 131.
Scheme 132.
Scheme 132.
Scheme 133.
Scheme 133.
Scheme 134.
Scheme 134.
Scheme 135.
Scheme 135.
Scheme 136.
Scheme 136.
Scheme 137.
Scheme 137.
Scheme 138.
Scheme 138.
Scheme 139.
Scheme 139.
Scheme 140.
Scheme 140.
Scheme 141.
Scheme 141.
Scheme 142.
Scheme 142.
Scheme 143.
Scheme 143.
Scheme 144.
Scheme 144.
Scheme 145.
Scheme 145.
Scheme 146.
Scheme 146.
Scheme 147.
Scheme 147.
Scheme 148.
Scheme 148.
Scheme 149.
Scheme 149.
Scheme 150.
Scheme 150.
Scheme 151.
Scheme 151.
Scheme 152.
Scheme 152.
Scheme 153.
Scheme 153.
Scheme 154.
Scheme 154.
Scheme 155.
Scheme 155.
Scheme 156.
Scheme 156.
Scheme 157.
Scheme 157.
Scheme 158.
Scheme 158.
Scheme 159.
Scheme 159.
Scheme 160.
Scheme 160.
Scheme 161.
Scheme 161.
Scheme 162.
Scheme 162.
Scheme 163.
Scheme 163.
Scheme 164.
Scheme 164.
Scheme 165.
Scheme 165.
Scheme 166.
Scheme 166.
Scheme 167.
Scheme 167.
Scheme 168.
Scheme 168.
Scheme 169.
Scheme 169.
Scheme 170.
Scheme 170.
Scheme 171.
Scheme 171.
Scheme 172.
Scheme 172.
Scheme 173.
Scheme 173.
Scheme 174.
Scheme 174.
Scheme 175.
Scheme 175.
Scheme 176.
Scheme 176.
Scheme 177.
Scheme 177.
Scheme 178.
Scheme 178.
Scheme 179.
Scheme 179.
Scheme 180.
Scheme 180.
Scheme 181.
Scheme 181.
Scheme 182.
Scheme 182.
Scheme 183.
Scheme 183.
Scheme 184.
Scheme 184.
Scheme 185.
Scheme 185.
Scheme 186.
Scheme 186.
Scheme 187.
Scheme 187.
Scheme 188.
Scheme 188.
Scheme 189.
Scheme 189.
Scheme 190.
Scheme 190.
Scheme 191.
Scheme 191.
Scheme 192.
Scheme 192.
Scheme 193.
Scheme 193.
Scheme 194.
Scheme 194.
Scheme 195.
Scheme 195.
Scheme 196.
Scheme 196.
Scheme 197.
Scheme 197.
Scheme 198.
Scheme 198.
Scheme 199.
Scheme 199.
Scheme 200.
Scheme 200.
Scheme 201.
Scheme 201.
Scheme 202.
Scheme 202.
Scheme 203.
Scheme 203.
Scheme 204.
Scheme 204.
Scheme 205.
Scheme 205.
Scheme 206.
Scheme 206.
Scheme 207.
Scheme 207.
Scheme 208.
Scheme 208.
Scheme 209.
Scheme 209.
Scheme 210.
Scheme 210.
Scheme 211.
Scheme 211.
Scheme 212.
Scheme 212.
Scheme 213.
Scheme 213.
Scheme 214.
Scheme 214.
Scheme 215.
Scheme 215.
Scheme 216.
Scheme 216.
Scheme 217.
Scheme 217.
Scheme 218.
Scheme 218.
Scheme 219.
Scheme 219.
Scheme 220.
Scheme 220.
Scheme 221.
Scheme 221.
Scheme 222.
Scheme 222.
Scheme 223.
Scheme 223.
Scheme 224.
Scheme 224.
Scheme 225.
Scheme 225.
Scheme 226.
Scheme 226.
Scheme 227.
Scheme 227.
Scheme 228.
Scheme 228.
Scheme 229.
Scheme 229.
Scheme 230.
Scheme 230.
Scheme 231.
Scheme 231.
Scheme 232.
Scheme 232.
Scheme 233.
Scheme 233.
Scheme 234.
Scheme 234.
Scheme 235.
Scheme 235.
Scheme 236.
Scheme 236.
Scheme 237.
Scheme 237.
Scheme 238.
Scheme 238.
Scheme 239.
Scheme 239.
Scheme 240.
Scheme 240.
Scheme 241.
Scheme 241.
Scheme 242.
Scheme 242.
Scheme 243.
Scheme 243.
Scheme 244.
Scheme 244.
Scheme 245.
Scheme 245.
Scheme 246.
Scheme 246.
Scheme 247.
Scheme 247.
Scheme 248.
Scheme 248.
Scheme 249.
Scheme 249.
Scheme 250.
Scheme 250.
Scheme 251.
Scheme 251.
Scheme 252.
Scheme 252.
Scheme 253.
Scheme 253.
Scheme 254.
Scheme 254.
Scheme 255.
Scheme 255.
Scheme 256.
Scheme 256.
Scheme 257.
Scheme 257.
Scheme 258.
Scheme 258.
Scheme 259.
Scheme 259.
Scheme 260.
Scheme 260.
Scheme 261.
Scheme 261.
Scheme 262.
Scheme 262.
Scheme 263.
Scheme 263.
Scheme 264.
Scheme 264.
Scheme 265.
Scheme 265.
Scheme 266.
Scheme 266.
Scheme 267.
Scheme 267.
Scheme 268.
Scheme 268.
Scheme 269.
Scheme 269.
Scheme 270.
Scheme 270.
Scheme 271.
Scheme 271.
Scheme 272.
Scheme 272.
Scheme 273.
Scheme 273.
Scheme 274.
Scheme 274.
Scheme 275.
Scheme 275.
Scheme 276.
Scheme 276.
Scheme 277.
Scheme 277.
Scheme 278.
Scheme 278.
Scheme 279.
Scheme 279.
Scheme 280.
Scheme 280.
Scheme 281.
Scheme 281.
Scheme 282.
Scheme 282.
Scheme 283.
Scheme 283.
Scheme 284.
Scheme 284.
Scheme 285.
Scheme 285.
Scheme 286.
Scheme 286.
Scheme 287.
Scheme 287.
Scheme 288.
Scheme 288.
Scheme 289.
Scheme 289.
Scheme 290.
Scheme 290.
Scheme 291.
Scheme 291.
Scheme 292.
Scheme 292.
Scheme 293.
Scheme 293.
Scheme 294.
Scheme 294.
Scheme 295.
Scheme 295.
Scheme 296.
Scheme 296.
Scheme 297.
Scheme 297.
Scheme 298.
Scheme 298.
Scheme 299.
Scheme 299.
Scheme 300.
Scheme 300.
Scheme 301.
Scheme 301.
Scheme 302.
Scheme 302.
Scheme 303.
Scheme 303.
Scheme 304.
Scheme 304.
Scheme 305.
Scheme 305.
Scheme 306.
Scheme 306.
Scheme 307.
Scheme 307.
Scheme 308.
Scheme 308.
Scheme 309.
Scheme 309.
Scheme 310.
Scheme 310.
Scheme 311.
Scheme 311.
Scheme 312.
Scheme 312.
Scheme 313.
Scheme 313.
Scheme 314.
Scheme 314.
Scheme 315.
Scheme 315.
Scheme 316.
Scheme 316.
Scheme 317.
Scheme 317.
Scheme 318.
Scheme 318.
Scheme 319.
Scheme 319.
Scheme 320.
Scheme 320.
Scheme 321.
Scheme 321.
Scheme 322.
Scheme 322.
Scheme 323.
Scheme 323.
Scheme 324.
Scheme 324.
Scheme 325.
Scheme 325.
Scheme 326.
Scheme 326.
Scheme 327.
Scheme 327.
Scheme 328.
Scheme 328.
Scheme 329.
Scheme 329.
Scheme 330.
Scheme 330.
Scheme 331.
Scheme 331.
Scheme 332.
Scheme 332.
Scheme 333.
Scheme 333.
Scheme 334.
Scheme 334.
Scheme 335.
Scheme 335.
Scheme 336.
Scheme 336.
Scheme 337.
Scheme 337.
Scheme 338.
Scheme 338.
Scheme 339.
Scheme 339.
Scheme 340.
Scheme 340.
Scheme 341.
Scheme 341.
Scheme 342.
Scheme 342.
Scheme 343.
Scheme 343.
Scheme 344.
Scheme 344.
Scheme 345.
Scheme 345.
Scheme 346.
Scheme 346.
Scheme 347.
Scheme 347.
Scheme 348.
Scheme 348.
Scheme 349.
Scheme 349.
Scheme 350.
Scheme 350.
Scheme 351.
Scheme 351.
Scheme 352.
Scheme 352.
Scheme 353.
Scheme 353.
Scheme 354.
Scheme 354.
Scheme 355.
Scheme 355.
Scheme 356.
Scheme 356.
Scheme 357.
Scheme 357.
Scheme 358.
Scheme 358.
Scheme 359.
Scheme 359.
Scheme 360.
Scheme 360.
Scheme 361.
Scheme 361.
Scheme 362.
Scheme 362.
Scheme 363.
Scheme 363.
Scheme 364.
Scheme 364.
Scheme 365.
Scheme 365.
Scheme 366.
Scheme 366.
Scheme 367.
Scheme 367.
Scheme 368.
Scheme 368.
Scheme 369.
Scheme 369.
Scheme 370.
Scheme 370.
Scheme 371.
Scheme 371.
Scheme 372.
Scheme 372.
Scheme 373.
Scheme 373.
Scheme 374.
Scheme 374.
Scheme 375.
Scheme 375.
Scheme 376.
Scheme 376.
Scheme 377.
Scheme 377.
Scheme 378.
Scheme 378.
Scheme 379.
Scheme 379.
Scheme 380.
Scheme 380.
Scheme 381.
Scheme 381.
Scheme 382.
Scheme 382.
Scheme 383.
Scheme 383.
Scheme 384.
Scheme 384.
Scheme 385.
Scheme 385.
Scheme 386.
Scheme 386.
Scheme 387.
Scheme 387.
Scheme 388.
Scheme 388.
Scheme 389.
Scheme 389.
Scheme 390.
Scheme 390.
Scheme 391.
Scheme 391.
Scheme 392.
Scheme 392.
Scheme 393.
Scheme 393.
Scheme 394.
Scheme 394.
Scheme 395.
Scheme 395.
Scheme 396.
Scheme 396.
Scheme 397.
Scheme 397.
Scheme 398.
Scheme 398.
Scheme 399.
Scheme 399.
Scheme 400.
Scheme 400.
Scheme 401.
Scheme 401.
Scheme 402.
Scheme 402.
Scheme 403.
Scheme 403.
Scheme 404.
Scheme 404.
Scheme 405.
Scheme 405.
Scheme 406.
Scheme 406.
Scheme 407.
Scheme 407.
Scheme 408.
Scheme 408.
Scheme 409.
Scheme 409.
Scheme 410.
Scheme 410.
Scheme 411.
Scheme 411.
Scheme 412.
Scheme 412.
Scheme 413.
Scheme 413.
Scheme 414.
Scheme 414.
Scheme 415.
Scheme 415.
Scheme 416.
Scheme 416.
Scheme 417.
Scheme 417.
Scheme 418.
Scheme 418.
Scheme 419.
Scheme 419.
Scheme 420.
Scheme 420.
Scheme 421.
Scheme 421.
Scheme 422.
Scheme 422.
Scheme 423.
Scheme 423.
Scheme 424.
Scheme 424.
Scheme 425.
Scheme 425.
Scheme 426.
Scheme 426.
Scheme 427.
Scheme 427.
Scheme 428.
Scheme 428.
Scheme 429.
Scheme 429.
Scheme 430.
Scheme 430.
Scheme 431.
Scheme 431.
Scheme 432.
Scheme 432.
Scheme 433.
Scheme 433.
Scheme 434.
Scheme 434.
Scheme 435.
Scheme 435.
Scheme 436.
Scheme 436.
Scheme 437.
Scheme 437.
Scheme 438.
Scheme 438.
Scheme 439.
Scheme 439.
Scheme 440.
Scheme 440.
Scheme 441.
Scheme 441.
Scheme 442.
Scheme 442.
Scheme 443.
Scheme 443.
Scheme 444.
Scheme 444.
Scheme 445.
Scheme 445.
Scheme 446.
Scheme 446.
Scheme 447.
Scheme 447.
Scheme 448.
Scheme 448.
Scheme 449.
Scheme 449.
Scheme 450.
Scheme 450.
Scheme 451.
Scheme 451.
Scheme 452.
Scheme 452.
Scheme 453.
Scheme 453.
Scheme 454.
Scheme 454.
Scheme 455.
Scheme 455.
Scheme 456.
Scheme 456.
Scheme 457.
Scheme 457.
Scheme 458.
Scheme 458.
Scheme 459.
Scheme 459.
Scheme 460.
Scheme 460.
Scheme 461.
Scheme 461.
Scheme 462.
Scheme 462.
See this image and copyright information in PMC

Similar articles

See all similar articles

Cited by

See all "Cited by" articles

References

    1. Yamamoto Y; Asao N Selective Reactions Using Allylic Metals. Chem. Rev 1993, 93, 2207–2293.
    1. Tatsuta K; Fukuda T; Ishimori T; Yachi R; Yoshida S; Hashimoto H; Hosokawa S The First Total Synthesis of Hibarimicinone, a Potent v-Src Tyrosine Kinase Inhibitor. Tetrahedron Lett. 2012, 53, 422–425.
    1. Bejjani J; Chemla F; Audouin M N-Tritylprolinal: An Efficient Building Block for the Stereoselective Synthesis of Proline-Derived Amino Alcohols. J. Org. Chem 2003, 68, 9747–9752. - PubMed
    1. Carda M; González F; Rodríguez S; Marco JA Highly Diastereoselective Additions of Organometallic Reagents to 1-O-Silylated 3,4-Di-O-Benzyl-l-Erythrulose Derivatives. Tetrahedron: Asymmetry 1993, 4, 1799–1802.
    1. Holt DJ; Barker WD; Jenkins PR; Davies DL; Garratt S; Fawcett J; Russell DR; Ghosh S Ring-Closing Metathesis in Carbohydrate Annulation. Angew. Chem. Int. Ed 1998, 37, 3298–3300. - PubMed

Publication types